Vessels, contact surfaces, and coating and inspection apparatus and methods

ABSTRACT

Methods for processing a contact surface, for example to provide a gas barrier or lubricity or to modify the wetting properties on a medical device, are disclosed. First and second PECVD or other contact surface processing stations or devices and a contact surface holder comprising a contact surface port are provided. An opening of the contact surface can be seated on the contact surface port. The interior contact surface of the seated contact surface can be processed via the contact surface port by the first and second processing stations or devices. contact surface barrier, lubricity and hydrophobic coatings and coated contact surfaces, for example syringes and medical sample collection tubes are disclosed. A contact surface processing system and contact surface inspection apparatus and methods are also disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the priority of U.S. Ser. No. 61/471,056, filedApr. 1, 2011, which is incorporated here by reference in its entirety.

The following patent applications, publications, and patents areincorporated here by reference in their entirety.

Application No. Filing Date Publication No. 61/177,984 May 13, 200961/222,727 Jul. 2, 2009 61/213,904 Jul. 24, 2009 61/234,505 Aug. 17,2009 61/261,321 Nov. 14, 2009 61/263,275 Nov. 20, 2009 61/263,289 Nov.20, 2009 61/285,813 Dec. 11, 2009 61/298,159 Jan. 25, 2010 61/299,888Jan. 29, 2010 61/318,197 Mar. 26, 2010 61/333,625 May 11, 201012/779,077 May 12, 2010 U.S. Pat. No. 7,985,188 EP10162755.2 May 12,2010 EP2253735A2 EP10162760.2 May 12, 2010 EP2251454A2 EP10162757.8 May12, 2010 EP2251453A2 EP10162756.0 May 12, 2010 EP2251452A2 EP10162758.6May 12, 2010 EP2251671A2 EP10162761.0 May 12, 2010 EP2251455A2PCT/US10/34568 May 12, 2010 WO 2010/132579 PCT/US10/34571 May 12, 2010WO 2010/132581 PCT/US10/34576 May 12, 2010 WO 2010/132584 PCT/US10/34577May 12, 2010 WO 2010/132585 PCT/US10/34582 May 12, 2010 WO 2010/132589PCT/US10/34586 May 12, 2010 WO/2010/132591 61/365,277 Jul. 16, 201061/371,967 Aug. 9, 2010 61/374,459 Aug. 17, 2010 61/379,299 Sep. 21,2010 61/413,329 Nov. 12, 2010 61/413,334 Nov. 12, 2010 61/413,355 Nov.12, 2010 61/413,340 Nov. 12, 2010 61/413,344 Nov. 12, 2010 61/413,347Nov. 12, 2010 61/452,526 Mar. 14, 2011 61/452,518 Mar. 14, 2011

The present invention relates to the technical field of fabrication ofcoated contact surfaces of a medical device, for example a vessel and/orother device for storing or contacting biologically active compounds orbody fluids. For example, the invention relates to a contact surfaceprocessing system for coating of a contact surface, a contact surfaceprocessing system for coating and inspection of a contact surface, aportable contact surface holder for a contact surface processing system,to a plasma enhanced chemical vapor deposition apparatus for coating acontact surface of a medical device, for example a vessel, to a methodfor coating an interior contact surface of a vessel, to a method forcoating and inspection of a vessel or contact surface, to a method ofprocessing a vessel or contact surface, to the use of a vessel orcontact surface processing system, to a computer-readable medium and toa program element.

The present disclosure also relates to improved methods for processingmedical devices, for example vessels, for example multiple identicalvessels used for venipuncture and other medical sample collection,pharmaceutical preparation storage and delivery, and other purposes.Such vessels or contact surfaces are used in large numbers for thesepurposes, and must be relatively economical to manufacture and yethighly reliable in storage and use.

BACKGROUND OF THE INVENTION

Evacuated blood collection tubes are used for drawing blood from apatient for medical analysis. The tubes are sold evacuated. Thepatient's blood is communicated to the interior of a tube by insertingone end of a double-ended hypodermic needle into the patient's bloodvessel and impaling the closure of the evacuated blood collection tubeon the other end of the double-ended needle. The vacuum in the evacuatedblood collection tube draws the blood (or more precisely, the bloodpressure of the patient pushes the blood) through the needle into theevacuated blood collection tube, increasing the pressure within the tubeand thus decreasing the pressure difference causing the blood to flow.The blood flow typically continues until the tube is removed from theneedle or the pressure difference is too small to support flow.

Evacuated blood collection tubes should have a substantial shelf life tofacilitate efficient and convenient distribution and storage of thetubes prior to use. For example, a one-year shelf life is desirable, andprogressively longer shelf lives, such as 18 months, 24 months, or 36months, are also desired in some instances. The tube desirably remainsessentially fully evacuated, at least to the degree necessary to drawenough blood for analysis (a common standard is that the tube retains atleast 90% of the original draw volume), for the full shelf life, withvery few (optimally no) defective tubes being provided.

A defective tube is likely to cause the phlebotomist using the tube tofail to draw sufficient blood. The phlebotomist might then need toobtain and use one or more additional tubes to obtain an adequate bloodsample.

Prefilled syringes are commonly prepared and sold so the syringe doesnot need to be filled before use. The syringe can be prefilled withsaline solution, a dye for injection, or a pharmaceutically activepreparation, for some examples.

Commonly, the prefilled syringe is capped at the distal end, as with acap, and is closed at the proximal end by its drawn plunger. Theprefilled syringe can be wrapped in a sterile package before use. To usethe prefilled syringe, the packaging and cap are removed, optionally ahypodermic needle or another delivery conduit is attached to the distalend of the barrel, the delivery conduit or syringe is moved to a useposition (such as by inserting the hypodermic needle into a patient'sblood vessel or into apparatus to be rinsed with the contents of thesyringe), and the plunger is advanced in the barrel to inject thecontents of the barrel.

One important consideration in manufacturing pre-filled syringes is thatthe contents of the syringe desirably will have a substantial shelflife, during which it is important to isolate the material filling thesyringe from the barrel wall containing it, to avoid leaching materialfrom the barrel into the prefilled contents or vice versa.

Since many of these vessels or contact surfaces are inexpensive and usedin large quantities, for certain applications it will be useful toreliably obtain the necessary shelf life without increasing themanufacturing cost to a prohibitive level. It is also desirable forcertain applications to move away from glass vessels or contactsurfaces, which can break and are expensive to manufacture, in favor ofplastic vessels or contact surfaces which are rarely broken in normaluse (and if broken do not form sharp shards from remnants of the vessel,like a glass tube would). Glass vessels have been favored because glassis more gas tight and inert to pre-filled contents than untreatedplastics. Also, due to its traditional use, glass is well accepted, asit is known to be relatively innocuous when contacted with medicalsamples or pharmaceutical preparations and the like.

A further consideration when regarding syringes is to ensure that theplunger can move at a constant speed and with a constant force when itis pressed into the barrel. For this purpose, a lubricity layer, eitheron one or on both of the barrel and the plunger, is desirable.

Similar considerations apply for other medical devices, particularlythose used in contact with a patient's tissue or body fluids, either invivo or in vitro. Many such devices have surfaces that require a barriercoating, lubricity, and/or a surface characteristic compatible with bodyfluids and tissues.

SUMMARY OF THE INVENTION

An aspect of the present invention is a medical device comprising asubstrate defining a contact surface and a lubricity layer deposited onthe contact surface. The contact surface is a point or area of contactbetween the substrate and a fluid or tissue when the medical device isin use. The lubricity layer is deposited on the contact surface andconfigured to provide a lower sliding force or breakout force for thecontact surface than for the uncoated substrate.

The lubricity layer has one of the following atomic ratios, measured byX-ray photoelectron spectroscopy (XPS), Si_(w)O_(x)C_(y) orSi_(w)N_(x)C_(y), where w is 1, x in this formula is from about 0.5 to2.4, and y is from about 0.6 to about 3. The lubricity layer has athickness by transmission electron microscopy (TEM) between 10 and 1000nm. The lubricity layer deposited by plasma enhanced chemical vapordeposition (PECVD) under conditions effective to form a coating from aprecursor. The precursor is selected from a linear siloxane, amonocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, alinear silazane, a monocyclic silazane, a polycyclic silazane, apolysilsesquiazane, a silatrane, a silquasilatrane, a silproatrane, anazasilatrane, an azasilquasiatrane, an azasilproatrane, or a combinationof any two or more of these precursors.

Another aspect of the invention is a medical device comprising asubstrate defining a contact surface as defined above and a barrierlayer deposited on the contact surface. The barrier layer is configuredto reduce the transmission of a fluid to or from the contact surface.

The barrier layer has one of the following atomic ratios, measured byX-ray photoelectron spectroscopy (XPS), SiO_(x) or SiN_(x), where x isfrom about 0.5 to 2.4. The barrier layer has a thickness by transmissionelectron microscopy (TEM) between 1 and 1000 nm. The barrier layer isdeposited by plasma enhanced chemical vapor deposition (PECVD) underconditions effective to form a coating from a precursor. As definedabove.

Still another aspect of the invention is a medical device comprisingcontact surface as previously defined. The contact surface is ahydrophobic layer having the composition: SiO_(x)C_(y) or SiN_(x)C_(y),where x in this formula is from about 0.5 to 2.4 and y is from about 0.6to about 3. The contact surface is of the type made by providing aprecursor as defined above, applying the precursor to a contact surface,and polymerizing or crosslinking the coating, or both, to form ahydrophobic contact surface having a higher contact angle than theuntreated contact surface.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic sectional view of a vessel holder in a coatingstation according to an embodiment of the disclosure.

FIG. 2 is an exploded longitudinal sectional view of a syringe and capadapted for use as a prefilled syringe.

FIG. 3 is a perspective view of a blood collection tube assembly havinga closure according to still another embodiment of the invention.

FIG. 4 is a fragmentary section of the blood collection tube and closureassembly of FIG. 3.

FIG. 5 is an isolated section of an elastomeric insert of the closure ofFIGS. 3 and 4.

FIG. 6 is a perspective view of a double-walled blood collection tubeassembly according to still another embodiment of the invention.

The following reference characters are used in the drawing figures:

28 Coating station 80 Vessel 82 Opening 84 Closed end 86 Wall 88Interior contact surface 90 Barrier layer 92 Vessel port 94 Vacuum duct96 Vacuum port 98 Vacuum source 100 O-ring (of 92) 102 O-ring (of 96)104 Gas inlet port 106 O-ring (of 100) 108 Probe (counter electrode) 110Gas delivery port (of 108) 114 Housing (of 50 or 112) 116 Collar 118Exterior contact surface (of 80) 144 PECVD gas source 160 Electrode 162Power supply 164 Sidewall (of 160) 166 Sidewall (of 160) 168 Closed end(of 160) 80 Vessel 84 Closed end 250 Syringe barrel 252 Syringe 254Interior contact surface (of 250) 256 Back end (of 250) 258 Plunger (of252) 260 Front end (of 250) 262 Cap 264 Interior contact surface (of262) 268 Vessel 270 Closure 272 Interior facing contact surface 274Lumen 276 Wall-contacting contact surface 278 Inner contact surface (of280) 280 Vessel wall 282 Stopper 284 Shield 286 Lubricity layer 288Barrier layer 408 Inner wall (FIG. 6) 410 Outer wall (FIG. 6) 412Interior contact surface (FIG. 6)

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention will now be described more fully with reference tothe accompanying drawings, in which several embodiments are shown. Thisinvention can, however, be embodied in many different forms and shouldnot be construed as limited to the embodiments set forth here. Rather,these embodiments are examples of the invention, which has the fullscope indicated by the language of the claims. Like numbers refer tolike or corresponding elements throughout.

DEFINITION SECTION

In the context of the present invention, the following definitions andabbreviations are used:

RF is radio frequency; sccm is standard cubic centimeters per minute.

The term “at least” in the context of the present invention means “equalor more” than the integer following the term. The word “comprising” doesnot exclude other elements or steps, and the indefinite article “a” or“an” does not exclude a plurality unless indicated otherwise.

“First” and “second” or similar references to, e.g., processing stationsor processing devices refer to the minimum number of processing stationsor devices that are present, but do not necessarily represent the orderor total number of processing stations and devices. These terms do notlimit the number of processing stations or the particular processingcarried out at the respective stations.

For purposes of the present invention, an “organosilicon precursor” is acompound having at least one of the linkage:

which is a tetravalent silicon atom connected to an oxygen atom and anorganic carbon atom (an organic carbon atom being a carbon atom bondedto at least one hydrogen atom). A volatile organosilicon precursor,defined as such a precursor that can be supplied as a vapor in a PECVDapparatus, is an optional organosilicon precursor. Optionally, theorganosilicon precursor is selected from the group consisting of alinear siloxane, a monocyclic siloxane, a polycyclic siloxane, apolysilsesquioxane, an alkyl trimethoxysilane, a linear silazane, amonocyclic silazane, a polycyclic silazane, a polysilsesquiazane, and acombination of any two or more of these precursors.

In the context of the present invention, “essentially no oxygen” or(synonymously) “substantially no oxygen” is added to the gaseousreactant in some embodiments. This means that some residual atmosphericoxygen can be present in the reaction space, and residual oxygen fed ina previous step and not fully exhausted can be present in the reactionspace, which are defined here as essentially no oxygen present.Essentially no oxygen is present in the gaseous reactant if the gaseousreactant comprises less than 1 vol. % O₂, for example less than 0.5 vol.% O₂, and optionally is O₂-free. If no oxygen is added to the gaseousreactant, or if no oxygen at all is present during PECVD, this is alsowithin the scope of “essentially no oxygen.”

A “vessel” in the context of the present invention is a subset exemplaryof the broader set of medical devices as defined herein. A vessel per secan be any type of article that is adapted to contain or convey amaterial. The material can be a liquid, a gas, a solid, or any two ormore of these. One example of a vessel is an article with at least oneopening and a wall defining an interior contact surface. Optionally, atleast a portion of the interior contact surface defines a “contactsurface” which is treated according to the present disclosure. The term“at least” in the context of the present invention means “equal or more”than the integer following the term. Thus, a vessel in the context ofthe present invention has one or more openings.

One or two openings, like the openings of a sample tube (one opening) ora syringe barrel (two openings) are preferred. If the vessel has two ormore openings, they can be of same or different size. If there is morethan one opening, one opening can be used for the gas inlet for a PECVDcoating method according to the present invention, while the otheropenings are either capped or open.

A vessel according to the present invention can be a sample tube, e.g.for collecting or storing biological fluids like blood or urine, asyringe (or a part thereof, for example a syringe barrel) for storing ordelivering a biologically active compound or composition, e.g. amedicament or pharmaceutical composition, a vial for storing biologicalmaterials or biologically active compounds or compositions, a pipe, e.g.a catheter for transporting biological materials or biologically activecompounds or compositions, or a cuvette for holding fluids, e.g. forholding biological materials or biologically active compounds orcompositions.

A vessel can be of any shape. One example of a vessel has asubstantially cylindrical wall adjacent to at least one of its openends. Generally, the interior wall of a vessel of this type iscylindrically shaped, like, e.g. in a sample tube or a syringe barrel.Sample tubes and syringes or their parts (for example syringe barrels),vials, and petri dishes, which commonly are generally cylindrical, arecontemplated.

Some other non-limiting examples of contemplated vessels include well ornon-well slides or plates, for example titer plates or microtiterplates. Still other non-limiting examples of contemplated vesselsinclude pump contact surfaces in contact with the pumped material,including impeller contact surfaces, pump chamber contact surfaces andthe like. Even other non-limiting examples of contemplated vesselsinclude parts of an fluid containment, pumping, processing, filtering,and delivery system, such as an intravenous fluid delivery system, ablood processing system (such as a heart-lung machine or a bloodcomponent separator) a dialysis system, or an insulin delivery system,as several examples. Examples of such vessel parts are tubing, pumpinterior contact surfaces, drug or saline containing bags or bottles,adapters and tubing connectors for connecting parts of the systemtogether, intravenous needles and needle assemblies, membranes andfilters, etc. Other examples of vessels include measuring and deliverydevices such as pipettes.

The invention has more general application to “contact surfaces” ofmedical devices and the like used or usable in contact with human oranimal fluids or tissues, whether or not associated with a vessel. Someadditional non-limiting examples of devices having contact surfaces aredevices inserted in an orifice, through the skin, or otherwise withinthe body of a human or animal, such as thermometers, probes, guidewires,catheters, electrical leads, surgical drains, pacemakers,defibrillators, orthopedic devices such as screws, plates, and rods,clothing, face masks, eye shields, and other equipment worn by medicalpersonnel, surgical drapes, sheet or fabric material used to make thesame, surgical instruments such as saws and saw blades, drills and drillbits, etc.

The invention further has application to any contact surfaces of devicesused or usable in contact with pharmaceutical preparations or othermaterials, such as ampoules, vials, syringes, bottles, bags, or othercontainment vessels, stirring rods, impellers, stirring pellets, etc.,also within the definition of “contact surfaces.”

Some specific medical devices having fluid or tissue contacting surfacesthat can be treated according to the present disclosure follow:

ACL/PCL Reconstruction Systems

Adapters

Adhesion barriers

Agar Petri dishes

Anesthesia units

Anesthesia ventilators

Angiographic Catheter

Ankle replacements

Aortic valve replacement

Apnea monitors

Applicators

Argon enhanced coagulation units

Artificial facet replacement

Artificial heart

Artificial heart valve

Artificial organ

Artificial pacemaker

Artificial pancreas

Artificial urinary bladder

Aspirators

Aspirators

Atherectomy Catheter

Auditory brainstem implant

Auto transfusion units

Bags

Balloon Catheter

Bare-metal stent

Beakers

bileaflet valves

Biliary Stent

Bio implants

Bioceramic devices

Bioresorbable stents

Biphasic Cuirass Ventilation

Blood Culture devices

Blood sample cassettes

Blood Sampling Systems

Bottles

Brain implant

Breast implant

Breast pumps

Buccal sample cassettes

Buttock augmentation

Caged-ball valves

Cannulated Screws

Capillary Blood Collection devices

Capsular contracture

Cardiac Catheter

Cardiac Catheter

Cardiac defibrillator, external or internal

Cardiac Output Injectate Kits & Cables

Cardiac prostheses

Cardiac shunt

Catheters

Cell lifters

Cell scrapers

Cell spreaders

Central Venous Catheter

Centrifuge components

Cerebral shunt

CHD Stent

Chemical transfer pumps

Chin augmentation

Chin sling

Cochlear implant

Collection and Transport devices

Colonic Stent

Compression pump

Connectors

Containers

Contraceptive implants

cornea implants

Coronary stents

Cotrel-Dubousset instrumentation

Cover glasses

Cranio Maxillofacial Implants

Cryo/Freezer boxes

Dehydrated Culture Media devices

Deltec Cozmo

Dental implants

Depression microscopic slides

Dewar flasks

DHS/DCS & Angled Blade Plates

Diabetes accessories

Diaphragm pumps

Diaphragmatic pacemaker

Direct Testing and Serology devices

Disposable Domes and Kits

Double Channel Catheter

Double-Lumen Catheter

Drug-Eluting Stents

Duodenal Stent

Dynamic compression plate

Dynamic hip screw

Elastomeric pump

Elbow replacements

Elbowed Catheter

Electrocardiograph (ECG)

Electrode Catheter

Electroencephalograph (EEG)

Electronic thermometer

Electrosurgical units

Endoscopes

Enteral feeding pumps

Environmental Systems devices

Esophageal stent

External Fixators

External pacemaker

Female Catheter

Fetal monitors

Films

Flat microscopic slides

Flow-restricted, oxygen-powered ventilation device

Fluid Administration Products

Fluid-Filled Catheter

Foley Catheter

Forceps

Glaucoma valve

Goggles

Gouley Catheter

grafts

Grommets

Gruentzig Balloon Catheter

Harrington rod

Heart valves

Heart-lung machine

HeartMate left ventricular assist device

Hip Prosthesis

Hip replacements

Hip resurfacing

Holders

Human-implantable RFID chips

Hypoxicator

Identification and Susceptibility devices

Implanon

Implant (medicine)

Implantable cardioverter-defibrillator

Implantable defibrilators

Implantable Devices

Implantable Gastric Stimulation

Incubators

Incubators

In-Dwelling Catheter

Infusion Sets

Inhaler

Insulin pen

Insulin pump

Insulin pumps

Interlocking Nail

Internal fixation

Intra-aortic balloon pump

Intramedullary rod

Intrathecal pump

Intrathecal pump

Intravenous Catheter

Invasive blood pressure units

Iron lung

IV Adapters

IV Catheters

IV Connectors

IV Flush Syringes

IV Products

IV Site Maintenance devices

IV Stopcocks

Joint replacement of the hand

Joint replacements

Keratometer

Kirschner wire

Knee cartilage replacement therapy

Knee replacements

Lancets

Laparoscopic insufflators

Large Fragment Implants

Lensometer

Liquid ventilator

Lytic bacteriophages

Medical grafting

Medical Pumps

Medical ventilator

Microbiology Equipment and Supplies

Microbiology Testing devices

Microchip implant (human)

Microscopic Slides

Microtiter plates

Midline Catheter

Mini dental implants

Mini Fragment Implants

Minimplants

Molecular Diagnostics devices

Mycobacteria Testing devices

Nails, Wires & Pins

Needleless IV Connectors

Nelaton urinary catheter

Norplant implantable birth control device

O'Neil Aspirating and Irrigating Needle

O'Neil Balloon Infuser

O'Neil Intermittent urinary catheter

Orthopedic implants

Osseointegration implant

Oxinium replacement joint material

Pacemakers

Pacing Catheter

Pain management pumps

Palatal obturator

Pancreatic Stent

Penile prosthesis

Penis enlargement device

Peripheral stents

Peripherally Inserted Central Catheter (PICC)

Peristaltic pumps

Peritoneovenous shunt

Petri dishes

Phonocardiographs

Phototherapy units

Pipettes

Polyaxial screw

Port (medical)

Portacaval shunt

Positive airway pressure device

Prepared Media devices

Pressure Accessories and Cables

Pressure Transducers

Prostatic Catheter

Prostatic stents

Pulmonary Artery Catheters

Pulse oximeters

radiant warmers

Radiation-therapy machines

Razor Blades

re-constructive prosthesis

Right-to-left shunt

Sacral nerve stimulator

Safety Supplies

Sample collection containers

Sample collection tubes

Sample Collection/Storage Devices

Self-expandable metallic stent Self-Retaining Catheter

Shaker flasks

Shoulder replacements

Shunt (medical)

skin implants

Small Fragment Implants

Snare Catheter

Sphygmomanometers

Spinal Cord Stimulator

Spine Surgery

Stains and Reagents

Static Control Supplies

Stent grafts

Stents

Sterility Supplies

Sterilizers

Stirrers

Subdermal implant

Surgical drill and saws

Surgical microscope

sutures

Swabs

Swan-Ganz Catheter

Syringe driver

Temperature monitor

Tenckhoff Catheter

Tiemann Catheter

tilting-disk valves

Tissue grinders

Toposcopic Catheter

Transdermal implant

Tubing

Tubing links

Two-Way Catheter

Ultrasonic nebulizers

Ultrasound sensors

Unicompartmental knee arthroplasty

Ureteral Catheter

Ureteral stents

Urethral Catheter

Urinary Catheter

Urine sample cassettes

Vascular ring connector

Vascular stents

Ventilator

Ventricular assist device

Vertebral fixation

Winged Catheter

X-ray diagnostic equipment

A “hydrophobic layer” in the context of the present invention means thatthe coating lowers the wetting tension of a contact surface coated withthe coating, compared to the corresponding uncoated contact surface.Hydrophobicity is thus a function of both the uncoated substrate and thecoating. The same applies with appropriate alterations for othercontexts wherein the term “hydrophobic” is used. The term “hydrophilic”means the opposite, i.e. that the wetting tension is increased comparedto reference sample. The present hydrophobic layers are primarilydefined by their hydrophobicity and the process conditions providinghydrophobicity, and optionally can have a composition according to theempirical composition or sum formula Si_(w)O_(x)C_(y)H_(z), for examplewhere w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 toabout 3, and z is from about 2 to about 9, optionally where w is 1, x isfrom about 0.5 to 1, y is from about 2 to about 3, and z is from 6 toabout 9. These values of w, x, y, and z are applicable to the empiricalcomposition Si_(w)O_(x)C_(y)H_(z) throughout this specification. Thevalues of w, x, y, and z used throughout this specification should beunderstood as ratios or an empirical formula (e.g. for a coating),rather than as a limit on the number or type of atoms in a molecule. Forexample, octamethylcyclotetrasiloxane, which has the molecularcomposition Si₄O₄C₈H₂₄, can be described by the following empiricalformula, arrived at by dividing each of w, x, y, and z in the molecularformula by 4, the largest common factor: Si₁O₁C₂H₆. The values of w, x,y, and z are also not limited to integers. For example, (acyclic)octamethyltrisiloxane, molecular composition Si₃O₂C₈H₂₄, is reducible toSi₁O_(0.67)C_(2.67)H₈.

“Wetting tension” is a specific measure for the hydrophobicity orhydrophilicity of a contact surface. An optional wetting tensionmeasurement method in the context of the present invention is ASTM D2578 or a modification of the method described in ASTM D 2578. Thismethod uses standard wetting tension solutions (called dyne solutions)to determine the solution that comes nearest to wetting a plastic filmcontact surface for exactly two seconds. This is the film's wettingtension. The procedure utilized is varied herein from ASTM D 2578 inthat the substrates are not flat plastic films, but are tubes madeaccording to the Protocol for Forming PET Tube and (except for controls)coated according to the Protocol for Coating Tube Interior withHydrophobic Layer (see Example 8).

A “lubricity layer” according to the present invention is a coatingwhich has a lower frictional resistance than the uncoated contactsurface. In other words, it reduces the frictional resistance of thecoated contact surface in comparison to a reference contact surfacewhich is uncoated. The present lubricity layers are primarily defined bytheir lower frictional resistance than the uncoated contact surface andthe process conditions providing lower frictional resistance than theuncoated contact surface, and optionally can have a compositionaccording to the empirical composition Si_(w)O_(x)C_(y)H_(z), as definedin this Definition Section. “Frictional resistance” can be staticfrictional resistance and/or kinetic frictional resistance. One of theoptional embodiments of the present invention is a syringe part, e.g. asyringe barrel or plunger, coated with a lubricity layer. In thiscontemplated embodiment, the relevant static frictional resistance inthe context of the present invention is the breakout force as definedherein, and the relevant kinetic frictional resistance in the context ofthe present invention is the plunger sliding force as defined herein.For example, the plunger sliding force as defined and determined hereinis suitable to determine the presence or absence and the lubricitycharacteristics of a lubricity layer in the context of the presentinvention whenever the coating is applied to any syringe or syringepart, for example to the inner wall of a syringe barrel. The breakoutforce is of particular relevance for evaluation of the coating effect ona prefilled syringe, i.e. a syringe which is filled after coating andcan be stored for some time, e.g. several months or even years, beforethe plunger is moved again (has to be “broken out”).

The “plunger sliding force” in the context of the present invention isthe force required to maintain movement of a plunger in a syringebarrel, e.g. during aspiration or dispense. It can advantageously bedetermined using the ISO 7886-1:1993 test described herein and known inthe art. A synonym for “plunger sliding force” often used in the art is“plunger force” or “pushing force”.

The “breakout force” in the context of the present invention is theinitial force required to move the plunger in a syringe, for example ina prefilled syringe.

Both “plunger sliding force” and “breakout force” and methods for theirmeasurement are described in more detail in subsequent parts of thisdescription.

“Slidably” means that the plunger is permitted to slide in a syringebarrel.

In the context of this invention, “substantially rigid” means that theassembled components (ports, duct, and housing, explained further below)can be moved as a unit by handling the housing, without significantdisplacement of any of the assembled components respecting the others.Specifically, none of the components are connected by hoses or the likethat allow substantial relative movement among the parts in normal use.The provision of a substantially rigid relation of these parts allowsthe location of the vessel seated on the vessel holder to be nearly aswell known and precise as the locations of these parts secured to thehousing

In the following, the apparatus for performing the present inventionwill be described first, followed by the coating methods, coatings andcoated vessels, and the uses according to the present invention.

Various aspects of:

vessel processing systems and equipment;

methods for transporting vessels—processing vessels seated on vesselholders;

PECVD apparatus for making vessels;

PECVD methods for making vessels; and

vessel inspection

are described in detail in U.S. Pat. No. 7,985,188 incorporated byreference above.

VII. PECVD Treated Vessels

VII. Vessels are contemplated having a barrier coating 90 (shown in FIG.1, for example), which can be an SiO_(x) coating applied to a thicknessof at least 2 nm, or at least 4 nm, or at least 7 nm, or at least 10 nm,or at least 20 nm, or at least 30 nm, or at least 40 nm, or at least 50nm, or at least 100 nm, or at least 150 nm, or at least 200 nm, or atleast 300 nm, or at least 400 nm, or at least 500 nm, or at least 600nm, or at least 700 nm, or at least 800 nm, or at least 900 nm. Thecoating can be up to 1000 nm, or at most 900 nm, or at most 800 nm, orat most 700 nm, or at most 600 nm, or at most 500 nm, or at most 400 nm,or at most 300 nm, or at most 200 nm, or at most 100 nm, or at most 90nm, or at most 80 nm, or at most 70 nm, or at most 60 nm, or at most 50nm, or at most 40 nm, or at most 30 nm, or at most 20 nm, or at most 10nm, or at most 5 nm thick. Specific thickness ranges composed of any oneof the minimum thicknesses expressed above, plus any equal or greaterone of the maximum thicknesses expressed above, are expresslycontemplated. The thickness of the SiO_(x) or other coating can bemeasured, for example, by transmission electron microscopy (TEM), andits composition can be measured by X-ray photoelectron spectroscopy(XPS).

VII. It is contemplated that the choice of the material to be barredfrom permeating the coating and the nature of the SiO_(x) coatingapplied can affect its barrier efficacy. For example, two examples ofmaterial commonly intended to be barred are oxygen and water/watervapor. Materials commonly are a better barrier to one than to the other.This is believed to be so at least in part because oxygen is transmittedthrough the coating by a different mechanism than water is transmitted.

VII. Oxygen transmission is affected by the physical features of thecoating, such as its thickness, the presence of cracks, and otherphysical details of the coating. Water transmission, on the other hand,is believed to commonly be affected by chemical factors, i.e. thematerial of which the coating is made, more than physical factors. Theinventors also believe that at least one of these chemical factors is asubstantial concentration of OH moieties in the coating, which leads toa higher transmission rate of water through the barrier. An SiO_(x)coating often contains OH moieties, and thus a physically sound coatingcontaining a high proportion of OH moieties is a better barrier tooxygen than to water. A physically sound carbon-based barrier, such asamorphous carbon or diamond-like carbon (DLC) commonly is a betterbarrier to water than is a SiO_(x) coating because the carbon-basedbarrier more commonly has a lower concentration of OH moieties.

VII. Other factors lead to a preference for an SiO_(x) coating, however,such as its oxygen barrier efficacy and its close chemical resemblanceto glass and quartz. Glass and quartz (when used as the base material ofa vessel) are two materials long known to present a very high barrier tooxygen and water transmission as well as substantial inertness to manymaterials commonly carried in vessels. Thus, it is commonly desirable tooptimize the water barrier properties such as the water vaportransmission rate (WVTR) of an SiO_(x) coating, rather than choosing adifferent or additional type of coating to serve as a water transmissionbarrier.

VII. Several ways contemplated to improve the WVTR of an SiO_(x) coatingare as follow.

VII. The concentration ratio of organic moieties (carbon and hydrogencompounds) to OH moieties in the deposited coating can be increased.This can be done, for example, by increasing the proportion of oxygen inthe feed gases (as by increasing the oxygen feed rate or by lowering thefeed rate of one or more other constituents). The lowered incidence ofOH moieties is believed to result from increasing the degree of reactionof the oxygen feed with the hydrogen in the silicone source to yieldmore volatile water in the PECVD exhaust and a lower concentration of OHmoieties trapped or incorporated in the coating.

VII. Higher energy can be applied in the PECVD process, either byraising the plasma generation power level, by applying the power for alonger period, or both. An increase in the applied energy must beemployed with care when used to coat a plastic tube or other device, asit also has a tendency to distort the vessel being treated, to theextent the tube absorbs the plasma generation power. This is why RFpower is contemplated in the context of present application. Distortionof the medical devices can be reduced or eliminated by employing theenergy in a series of two or more pulses separated by cooling time, bycooling the vessels while applying energy, by applying the coating in ashorter time (commonly thus making it thinner), by selecting a frequencyof the applied coating that is absorbed minimally by the base materialselected for being coated, and/or by applying more than one coating,with time in between the respective energy application steps. Forexample, high power pulsing can be used with a duty cycle of 1millisecond on, 99 milliseconds off, while continuing to feed theprocess gas. The process gas is then the coolant, as it keeps flowingbetween pulses. Another alternative is to reconfigure the powerapplicator, as by adding magnets to confine the plasma increase theeffective power application (the power that actually results inincremental coating, as opposed to waste power that results in heatingor unwanted coating). This expedient results in the application of morecoating-formation energy per total Watt-hour of energy applied. See forexample U.S. Pat. No. 5,904,952.

VII. An oxygen post-treatment of the coating can be applied to remove OHmoieties from the previously-deposited coating. This treatment is alsocontemplated to remove residual volatile organosilicon compounds orsilicones or oxidize the coating to form additional SiO_(x).

VII. The plastic base material tube can be preheated.

VII. A different volatile source of silicon, such ashexamethyldisilazane (HMDZ), can be used as part or all of the siliconefeed. It is contemplated that changing the feed gas to HMDZ will addressthe problem because this compound has no oxygen moieties in it, assupplied. It is contemplated that one source of OH moieties in theHMDSO-sourced coating is hydrogenation of at least some of the oxygenatoms present in unreacted HMDSO.

VII. A composite coating can be used, such as a carbon-based coatingcombined with SiO_(x). This can be done, for example, by changing thereaction conditions or by adding a substituted or unsubstitutedhydrocarbon, such as an alkane, alkene, or alkyne, to the feed gas aswell as an organosilicon-based compound. See for example U.S. Pat. No.5,904,952, which states in relevant part: “For example, inclusion of alower hydrocarbon such as propylene provides carbon moieties andimproves most properties of the deposited films (except for lighttransmission), and bonding analysis indicates the film to be silicondioxide in nature. Use of methane, methanol, or acetylene, however,produces films that are silicone in nature. The inclusion of a minoramount of gaseous nitrogen to the gas stream provides nitrogen moietiesin the deposited films and increases the deposition rate, improves thetransmission and reflection optical properties on glass, and varies theindex of refraction in response to varied amounts of N₂. The addition ofnitrous oxide to the gas stream increases the deposition rate andimproves the optical properties, but tends to decrease the filmhardness.”

VII. A diamond-like carbon (DLC) coating can be formed as the primary orsole coating deposited. This can be done, for example, by changing thereaction conditions or by feeding methane, hydrogen, and helium to aPECVD process. These reaction feeds have no oxygen, so no OH moietiescan be formed. For one example, an SiO_(x) coating can be applied on theinterior of a tube or syringe barrel and an outer DLC coating can beapplied on the exterior contact surface of a tube or syringe barrel. Or,the SiO_(x) and DLC coatings can both be applied as a single layer orplural layers of an interior tube or syringe barrel coating.

VII. Referring to FIG. 1, the barrier or other type of coating 90reduces the transmission of atmospheric gases into the vessel 80 throughits interior contact surface 88. Or, the barrier or other type ofcoating 90 reduces the contact of the contents of the vessel 80 with theinterior contact surface 88. The barrier or other type of coating cancomprise, for example, SiO_(x), amorphous (for example, diamond-like)carbon, or a combination of these.

VII. Any coating described herein can be used for coating a contactsurface, for example a plastic contact surface. It can further be usedas a barrier layer, for example as a barrier against a gas or liquid,optionally against water vapor, oxygen and/or air. It can also be usedfor preventing or reducing mechanical and/or chemical effects which thecoated contact surface would have on a compound or composition if thecontact surface were uncoated. For example, it can prevent or reduce theprecipitation of a compound or composition, for example insulinprecipitation or blood clotting or platelet activation.

VII.A. Evacuated Blood Collection Vessels VII.A.1. Tubes

VII.A.I. Referring to FIG. 1, more details of the vessel such as 80 areshown. The illustrated vessel 80 can be generally tubular, having anopening 82 at one end of the vessel, opposed by a closed end 84. Thevessel 80 also has a wall 86 defining an interior contact surface 88.One example of the vessel 80 is a medical sample tube, such as anevacuated blood collection tube, as commonly is used by a phlebotomistfor receiving a venipuncture sample of a patient's blood for use in amedical laboratory.

VII.A.1. The vessel 80 can be made, for example, of thermoplasticmaterial. Some examples of suitable thermoplastic material arepolyethylene terephthalate or a polyolefin such as polypropylene or acyclic polyolefin copolymer.

VII.A.1. The vessel 80 can be made by any suitable method, such as byinjection molding, by blow molding, by machining, by fabrication fromtubing stock, or by other suitable means. PECVD can be used to form acoating on the internal contact surface of SiO_(x).

VII.A.1. If intended for use as an evacuated blood collection tube, thevessel 80 desirably can be strong enough to withstand a substantiallytotal internal vacuum substantially without deformation when exposed toan external pressure of 760 Torr or atmospheric pressure and othercoating processing conditions. This property can be provided, in athermoplastic vessel 80, by providing a vessel 80 made of suitablematerials having suitable dimensions and a glass transition temperaturehigher than the processing temperature of the coating process, forexample a cylindrical wall 86 having sufficient wall thickness for itsdiameter and material.

VII.A.1. Medical vessels or containers like sample collection tubes andsyringes are relatively small and are injection molded with relativelythick walls, which renders them able to be evacuated without beingcrushed by the ambient atmospheric pressure. They are thus stronger thancarbonated soft drink bottles or other larger or thinner-walled plasticcontainers. Since sample collection tubes designed for use as evacuatedvessels typically are constructed to withstand a full vacuum duringstorage, they can be used as vacuum chambers.

VII.A.1. Such adaptation of the vessels to be their own vacuum chambersmight eliminate the need to place the vessels into a vacuum chamber forPECVD treatment, which typically is carried out at very low pressure.The use of a vessel as its own vacuum chamber can result in fasterprocessing time (since loading and unloading of the parts from aseparate vacuum chamber is not necessary) and can lead to simplifiedequipment configurations. Furthermore, a vessel holder is contemplated,for certain embodiments, that will hold the device (for alignment to gastubes and other apparatus), seal the device (so that the vacuum can becreated by attaching the vessel holder to a vacuum pump) and move thedevice between molding and subsequent processing steps.

VII.A.1. A vessel 80 used as an evacuated blood collection tube shouldbe able to withstand external atmospheric pressure, while internallyevacuated to a reduced pressure useful for the intended application,without a substantial volume of air or other atmospheric gas leakinginto the tube (as by bypassing the closure) or permeating through thewall 86 during its shelf life. If the as-molded vessel 80 cannot meetthis requirement, it can be processed by coating the interior contactsurface 88 with a barrier or other type of coating 90. It is desirableto treat and/or coat the interior contact surfaces of these devices(such as sample collection tubes and syringe barrels) to impart variousproperties that will offer advantages over existing polymeric devicesand/or to mimic existing glass products. It is also desirable to measurevarious properties of the devices before and/or after treatment orcoating.

VII.A.1.a. Coating Deposited from an Organosilicon Precursor Made by InSitu Polymerizing Organosilicon Precursor

VII.A.1.a. A process is contemplated for applying a lubricity layercharacterized as defined in the Definition Section on a substrate, forexample the interior of the barrel of a syringe, comprising applying oneof the described precursors on or in the vicinity of a substrate at athickness of 1 to 5000 nm, optionally 10 to 1000 nm, optionally 10-200nm, optionally 20 to 100 nm thick and crosslinking or polymerizing (orboth) the coating, optionally in a PECVD process, to provide alubricated contact surface. The coating applied by this process is alsocontemplated to be new.

VII.A.1.a. A coating of Si_(w)O_(x)C_(y)H_(z) as defined in theDefinition Section can have utility as a hydrophobic layer. Coatings ofthis kind are contemplated to be hydrophobic, independent of whetherthey function as lubricity layers. A coating or treatment is defined as“hydrophobic” if it lowers the wetting tension of a contact surface,compared to the corresponding uncoated or untreated contact surface.Hydrophobicity is thus a function of both the untreated substrate andthe treatment.

VII.A.1.a. The degree of hydrophobicity of a coating can be varied byvarying its composition, properties, or deposition method. For example,a coating of SiO_(x) having little or no hydrocarbon content is morehydrophilic than a coating of Si_(w)O_(x)C_(y)H_(z) as defined in theDefinition Section. Generally speaking, the higher the C—H_(x) (e.g. CH,CH₂, or CH₃) moiety content of the coating, either by weight, volume, ormolarity, relative to its silicon content, the more hydrophobic thecoating.

VII.A.1.a. A hydrophobic layer can be very thin, having a thickness ofat least 4 nm, or at least 7 nm, or at least 10 nm, or at least 20 nm,or at least 30 nm, or at least 40 nm, or at least 50 nm, or at least 100nm, or at least 150 nm, or at least 200 nm, or at least 300 nm, or atleast 400 nm, or at least 500 nm, or at least 600 nm, or at least 700nm, or at least 800 nm, or at least 900 nm. The coating can be up to1000 nm, or at most 900 nm, or at most 800 nm, or at most 700 nm, or atmost 600 nm, or at most 500 nm, or at most 400 nm, or at most 300 nm, orat most 200 nm, or at most 100 nm, or at most 90 nm, or at most 80 nm,or at most 70 nm, or at most 60 nm, or at most 50 nm, or at most 40 nm,or at most 30 nm, or at most 20 nm, or at most 10 nm, or at most 5 nmthick. Specific thickness ranges composed of any one of the minimumthicknesses expressed above, plus any equal or greater one of themaximum thicknesses expressed above, are expressly contemplated.

VII.A.1.a. One utility for such a hydrophobic layer is to isolate athermoplastic tube wall, made for example of polyethylene terephthalate(PET), from blood collected within the tube. The hydrophobic layer canbe applied on top of a hydrophilic SiO_(x) coating on the internalcontact surface of the tube. The SiO_(x) coating increases the barrierproperties of the thermoplastic tube and the hydrophobic layer changesthe contact surface energy of blood contact surface with the tube wall.The hydrophobic layer can be made by providing a precursor selected fromthose identified in this specification. For example, the hydrophobiclayer precursor can comprise hexamethyldisiloxane (HMDSO) oroctamethylcyclotetrasiloxane (OMCTS).

VII.A.1.a. Another use for a hydrophobic layer is to prepare a glasscell preparation tube. The tube has a wall defining a lumen, ahydrophobic layer in the internal contact surface of the glass wall, andcontains a citrate reagent. The hydrophobic layer can be made byproviding a precursor selected from those identified elsewhere in thisspecification. For another example, the hydrophobic layer precursor cancomprise hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane(OMCTS). Another source material for hydrophobic layers is an alkyltrimethoxysilane of the formula:

R—Si(OCH₃)₃

in which R is a hydrogen atom or an organic substituent, for examplemethyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl,alkyne, epoxide, or others. Combinations of two or more of these arealso contemplated.

VII.A.1.a. Combinations of acid or base catalysis and heating, using analkyl trimethoxysilane precursor as described above, can condense theprecursor (removing ROH by-products) to form crosslinked polymers, whichcan optionally be further crosslinked via an alternative method. Onespecific example is by Shimojima et. al. J. Mater. Chem., 2007, 17,658-663.

VII.A.1.a. A lubricity layer, characterized as defined in the DefinitionSection, can be applied as a subsequent coating after applying anSiO_(x) barrier coating to the interior contact surface 88 of the vessel80 to provide a lubricity layer, particularly if the lubricity layer isa liquid organosiloxane compound at the end of the coating process.

VII.A.1.a. Optionally, after the lubricity layer is applied, it can bepost-cured after the PECVD process. Radiation curing approaches,including UV-initiated (free radial or cationic), electron-beam(E-beam), and thermal as described in Development Of NovelCycloaliphatic Siloxanes For Thermal And UV-Curable Applications (RubyChakraborty Dissertation, can 2008) be utilized.

VII.A.1.a. Another approach for providing a lubricity layer is to use asilicone demolding agent when injection-molding the thermoplastic vesselto be lubricated. For example, it is contemplated that any of thedemolding agents and latent monomers causing in-situ thermal lubricitylayer formation during the molding process can be used. Or, theaforementioned monomers can be doped into traditional demolding agentsto accomplish the same result.

VII.A.1.a. A lubricity layer, characterized as defined in the DefinitionSection, is particularly contemplated for the internal contact surfaceof a syringe barrel as further described below. A lubricated internalcontact surface of a syringe barrel can reduce the plunger sliding forceneeded to advance a plunger in the barrel during operation of a syringe,or the breakout force to start a plunger moving after the prefilledsyringe plunger has pushed away the intervening lubricant or adhered tothe barrel, for example due to decomposition of the lubricant betweenthe plunger and the barrel. As explained elsewhere in thisspecification, a lubricity layer also can be applied to the interiorcontact surface 88 of the vessel 80 to improve adhesion of a subsequentcoating of SiO_(x).

VII.A.1.a. Thus, the coating 90 can comprise a layer of SiO_(x) and alubricity layer and/or hydrophobic layer, characterized as defined inthe Definition Section. The lubricity layer and/or hydrophobic layer ofSi_(w)O_(x)C_(y)H_(z) can be deposited between the layer of SiO_(x) andthe interior contact surface of the vessel. Or, the layer of SiO_(x) canbe deposited between the lubricity layer and/or hydrophobic layer andthe interior contact surface of the vessel. Or, three or more layers,either alternating or graduated between these two coating compositions:(1) a layer of SiO_(x) and (2) the lubricity layer and/or hydrophobiclayer; can also be used. The layer of SiO_(x) can be deposited adjacentto the lubricity layer and/or hydrophobic layer or remotely, with atleast one intervening layer of another material. The layer of SiO_(x)can be deposited adjacent to the interior contact surface of the vessel.Or, the lubricity layer and/or hydrophobic layer can be depositedadjacent to the interior contact surface of the vessel.

VII.A.1.a. Another expedient contemplated here, for adjacent layers ofSiO_(x) and a lubricity layer and/or hydrophobic layer, is a gradedcomposite of Si_(w)O_(x)C_(y)H_(z), as defined in the DefinitionSection. A graded composite can be separate layers of a lubricity layerand/or hydrophobic layer and SiO_(x) with a transition or interface ofintermediate composition between them, or separate layers of a lubricitylayer and/or hydrophobic layer and SiO_(x) with an intermediate distinctlayer of intermediate composition between them, or a single layer thatchanges continuously or in steps from a composition of a lubricity layerand/or hydrophobic layer to a composition more like SiO_(x), goingthrough the coating in a normal direction.

VII.A.1.a. The grade in the graded composite can go in either direction.For example, the a lubricity layer and/or hydrophobic layer can beapplied directly to the substrate and graduate to a composition furtherfrom the contact surface of SiO_(x). Or, the composition of SiO_(x) canbe applied directly to the substrate and graduate to a compositionfurther from the contact surface of a lubricity layer and/or hydrophobiclayer. A graduated coating is particularly contemplated if a coating ofone composition is better for adhering to the substrate than the other,in which case the better-adhering composition can, for example, beapplied directly to the substrate. It is contemplated that the moredistant portions of the graded coating can be less compatible with thesubstrate than the adjacent portions of the graded coating, since at anypoint the coating is changing gradually in properties, so adjacentportions at nearly the same depth of the coating have nearly identicalcomposition, and more widely physically separated portions atsubstantially different depths can have more diverse properties. It isalso contemplated that a coating portion that forms a better barrieragainst transfer of material to or from the substrate can be directlyagainst the substrate, to prevent the more remote coating portion thatforms a poorer barrier from being contaminated with the materialintended to be barred or impeded by the barrier.

VII.A.1.a. The coating, instead of being graded, optionally can havesharp transitions between one layer and the next, without a substantialgradient of composition. Such coatings can be made, for example, byproviding the gases to produce a layer as a steady state flow in anon-plasma state, then energizing the system with a brief plasmadischarge to form a coating on the substrate. If a subsequent coating isto be applied, the gases for the previous coating are cleared out andthe gases for the next coating are applied in a steady-state fashionbefore energizing the plasma and again forming a distinct layer on thecontact surface of the substrate or its outermost previous coating, withlittle if any gradual transition at the interface.

VII.A.1.b. Citrate Blood Tube Having Wall Coated with Hydrophobic LayerDeposited from an Organosilicon Precursor

VII.A.1.b. Another embodiment is a cell preparation tube having a wallprovided with a hydrophobic layer on its inside contact surface andcontaining an aqueous sodium citrate reagent. The hydrophobic layer canbe also be applied on top of a hydrophilic SiO_(x) coating on theinternal contact surface of the tube. The SiO_(x) coating increases thebarrier properties of the thermoplastic tube and the hydrophobic layerchanges the contact surface energy of blood contact surface with thetube wall.

VII.A.1.b. The wall is made of thermoplastic material having an internalcontact surface defining a lumen.

VII.A.1.b. A blood collection tube according to the embodiment VII.A.1.bcan have a first layer of SiO_(x) on the internal contact surface of thetube, applied as explained in this specification, to function as anoxygen barrier and extend the shelf life of an evacuated bloodcollection tube made of thermoplastic material. A second layer of ahydrophobic layer, characterized as defined in the Definition Section,can then be applied over the barrier layer on the internal contactsurface of the tube to provide a hydrophobic contact surface. Thecoating is effective to reduce the platelet activation of blood plasmatreated with a sodium citrate additive and exposed to the inner contactsurface, compared to the same type of wall uncoated.

VII.A.1.b. PECVD is used to form a hydrophobic layer on the internalcontact surface, characterized as defined in the Definition Section.Unlike conventional citrate blood collection tubes, the blood collectiontube having a hydrophobic layer, characterized as defined in theDefinition Section does not require a coating of baked on silicone onthe vessel wall, as is conventionally applied to make the contactsurface of the tube hydrophobic.

VII.A.1.b. Both layers can be applied using the same precursor, forexample HMDSO or OMCTS, and different PECVD reaction conditions.

VII.A.1.b. A sodium citrate anticoagulation reagent is then placedwithin the tube and it is evacuated and sealed with a closure to producean evacuated blood collection tube. The components and formulation ofthe reagent are known to those skilled in the art. The aqueous sodiumcitrate reagent is disposed in the lumen of the tube in an amounteffective to inhibit coagulation of blood introduced into the tube.

VII.A.1.c. SiO_(x) Barrier Coated Double Wall Plastic Vessel—COC, PET,SiO_(x) Layers

VII.A.1.c. Another embodiment is a vessel having a wall at leastpartially enclosing a lumen. The wall has an interior polymer layerenclosed by an exterior polymer layer. One of the polymer layers is alayer at least 0.1 mm thick of a cyclic olefin copolymer (COC) resindefining a water vapor barrier. Another of the polymer layers is a layerat least 0.1 mm thick of a polyester resin.

VII.A.1.c. The wall includes an oxygen barrier layer of SiO_(x) having athickness of from about 10 to about 500 angstroms.

VII.A.1.c. In an embodiment, illustrated in FIG. 6, the vessel 80 can bea double-walled vessel having an inner wall 408 and an outer wall 410,respectively made of the same or different materials. One particularembodiment of this type can be made with one wall molded from a cyclicolefin copolymer (COC) and the other wall molded from a polyester suchas polyethylene terephthalate (PET), with an SiO_(x) coating aspreviously described on the interior contact surface 412. As needed, atie coating or layer can be inserted between the inner and outer wallsto promote adhesion between them. An advantage of this wall constructionis that walls having different properties can be combined to form acomposite having the respective properties of each wall.

VII.A.1.c. As one example, the inner wall 408 can be made of PET coatedon the interior contact surface 412 with an SiO_(x) barrier layer, andthe outer wall 410 can be made of COC. PET coated with SiO_(x), as shownelsewhere in this specification, is an excellent oxygen barrier, whileCOC is an excellent barrier for water vapor, providing a low water vaportransition rate (WVTR). This composite vessel can have superior barrierproperties for both oxygen and water vapor. This construction iscontemplated, for example, for an evacuated medical sample collectiontube that contains an aqueous reagent as manufactured, and has asubstantial shelf life, so it should have a barrier preventing transferof water vapor outward or transfer of oxygen or other gases inwardthrough its composite wall during its shelf life.

VII.A.1.c. As another example, the inner wall 408 can be made of COCcoated on the interior contact surface 412 with an SiO_(x) barrierlayer, and the outer wall 410 can be made of PET. This construction iscontemplated, for example, for a prefilled syringe that contains anaqueous sterile fluid as manufactured. The SiO_(x) barrier will preventoxygen from entering the syringe through its wall. The COC inner wallwill prevent ingress or egress of other materials such as water, thuspreventing the water in the aqueous sterile fluid from leachingmaterials from the wall material into the syringe. The COC inner wall isalso contemplated to prevent water derived from the aqueous sterilefluid from passing out of the syringe (thus undesirably concentratingthe aqueous sterile fluid), and will prevent non-sterile water or otherfluids outside the syringe from entering through the syringe wall andcausing the contents to become non-sterile. The COC inner wall is alsocontemplated to be useful for decreasing the breaking force or frictionof the plunger against the inner wall of a syringe.

VII.A.1.d. Method of Making Double Wall Plastic Vessel—COC, PET, SiO_(x)Layers

VII.A.1.d. Another embodiment is a method of making a vessel having awall having an interior polymer layer enclosed by an exterior polymerlayer, one layer made of COC and the other made of polyester. The vesselis made by a process including introducing COC and polyester resinlayers into an injection mold through concentric injection nozzles.

VII.A.1.d. An optional additional step is applying an amorphous carboncoating to the vessel by PECVD, as an inside coating, an outsidecoating, or as an interlayer coating located between the layers.

VII.A.1.d. An optional additional step is applying an SiO_(x) barrierlayer to the inside of the vessel wall, where SiO_(x) is defined asbefore. Another optional additional step is post-treating the SiO_(x)layer with a process gas consisting essentially of oxygen andessentially free of a volatile silicon compound.

VII.A.1.d. Optionally, the SiO_(x) coating can be formed at leastpartially from a silazane feed gas.

VII.A.1.d. The vessel 80 shown in FIG. 6 can be made from the insideout, for one example, by injection molding the inner wall in a firstmold cavity, then removing the core and molded inner wall from the firstmold cavity to a second, larger mold cavity, then injection molding theouter wall against the inner wall in the second mold cavity. Optionally,a tie layer can be provided to the exterior contact surface of themolded inner wall before over-molding the outer wall onto the tie layer.

VII.A.1.d. Or, the vessel 80 shown in FIG. 6 can be made from theoutside in, for one example, by inserting a first core in the moldcavity, injection molding the outer wall in the mold cavity, thenremoving the first core from the molded first wall and inserting asecond, smaller core, then injection molding the inner wall against theouter wall still residing in the mold cavity. Optionally, a tie layercan be provided to the interior contact surface of the molded outer wallbefore over-molding the inner wall onto the tie layer.

VII.A.1.d. Or, the vessel 80 shown in FIG. 6 can be made in a two shotmold. This can be done, for one example, by injection molding materialfor the inner wall from an inner nozzle and the material for the outerwall from a concentric outer nozzle. Optionally, a tie layer can beprovided from a third, concentric nozzle disposed between the inner andouter nozzles. The nozzles can feed the respective wall materialssimultaneously. One useful expedient is to begin feeding the outer wallmaterial through the outer nozzle slightly before feeding the inner wallmaterial through the inner nozzle. If there is an intermediateconcentric nozzle, the order of flow can begin with the outer nozzle andcontinue in sequence from the intermediate nozzle and then from theinner nozzle. Or, the order of beginning feeding can start from theinside nozzle and work outward, in reverse order compared to thepreceding description.

VII.A.1.e. Barrier Coating Made of Glass

VII.A.1.e. Another embodiment is a vessel including a barrier coatingand a closure. The vessel is generally tubular and made of thermoplasticmaterial. The vessel has a mouth and a lumen bounded at least in part bya wall having an inner contact surface interfacing with the lumen. Thereis an at least essentially continuous barrier coating made of glass onthe inner contact surface of the wall. A closure covers the mouth andisolates the lumen of the vessel from ambient air.

VII.A.1.e. The vessel 80 can also be made, for example of glass of anytype used in medical or laboratory applications, such as soda-limeglass, borosilicate glass, or other glass formulations. Other vesselshaving any shape or size, made of any material, are also contemplatedfor use in the system 20. One function of coating a glass vessel can beto reduce the ingress of ions in the glass, either intentionally or asimpurities, for example sodium, calcium, or others, from the glass tothe contents of the vessel, such as a reagent or blood in an evacuatedblood collection tube. Another function of coating a glass vessel inwhole or in part, such as selectively at contact surfaces contacted insliding relation to other parts, is to provide lubricity to the coating,for example to ease the insertion or removal of a stopper or passage ofa sliding element such as a piston in a syringe. Still another reason tocoat a glass vessel is to prevent a reagent or intended sample for thevessel, such as blood, from sticking to the wall of the vessel or anincrease in the rate of coagulation of the blood in contact with thewall of the vessel.

VII.A.1.e.i. A related embodiment is a vessel as described in theprevious paragraph, in which the barrier coating is made of soda limeglass, borosilicate glass, or another type of glass.

VII.A.2. Stoppers

VII.A.2. FIGS. 3-5 illustrate a vessel 268, which can be an evacuatedblood collection tube, having a closure 270 to isolate the lumen 274from the ambient environment. The closure 270 comprises ainterior-facing contact surface 272 exposed to the lumen 274 of thevessel 268 and a wall-contacting contact surface 276 that is in contactwith the inner contact surface 278 of the vessel wall 280. In theillustrated embodiment the closure 270 is an assembly of a stopper 282and a shield 284.

VII.A.2.a. Method of Applying Lubricity Layer to Stopper in VacuumChamber

VII.A.2.a. Another embodiment is a method of applying a coating on anelastomeric stopper such as 282. The stopper 282, separate from thevessel 268, is placed in a substantially evacuated chamber. A reactionmixture is provided including plasma forming gas, i.e. an organosiliconcompound gas, optionally an oxidizing gas, and optionally a hydrocarbongas. Plasma is formed in the reaction mixture, which is contacted withthe stopper. A lubricity and/or hydrophobic layer, characterized asdefined in the Definition Section, is deposited on at least a portion ofthe stopper.

VII.A.2.a. In the illustrated embodiment, the wall-contacting contactsurface 276 of the closure 270 is coated with a lubricity layer 286.

VII.A.2.a. In some embodiments, the lubricity and/or hydrophobic layer,characterized as defined in the Definition Section, is effective toreduce the transmission of one or more constituents of the stopper, suchas a metal ion constituent of the stopper, or of the vessel wall, intothe vessel lumen. Certain elastomeric compositions of the type usefulfor fabricating a stopper 282 contain trace amounts of one or more metalions. These ions sometimes should not be able to migrate into the lumen274 or come in substantial quantities into contact with the vesselcontents, particularly if the sample vessel 268 is to be used to collecta sample for trace metal analysis. It is contemplated for example thatcoatings containing relatively little organic content, i.e. where y andz of Si_(w)O_(x)C_(y)H_(z) as defined in the Definition Section are lowor zero, are particularly useful as a metal ion barrier in thisapplication. Regarding silica as a metal ion barrier see, for example,Anupama Mallikarjunan, Jasbir Juneja, Guangrong Yang, Shyam P. Murarka,and Toh-Ming Lu, The Effect of Interfacial Chemistry on Metal IonPenetration into Polymeric Films, Mat. Res. Soc. Symp. Proc., Vol. 734,pp. B9.60.1 to B9.60.6 (Materials Research Society, 2003); U.S. Pat.Nos. 5,578,103 and 6,200,658, and European Appl. EP0697378 A2, which areall incorporated here by reference. It is contemplated, however, thatsome organic content can be useful to provide a more elastic coating andto adhere the coating to the elastomeric contact surface of the stopper282.

VII.A.2.a. In some embodiments, the lubricity and/or hydrophobic layer,characterized as defined in the Definition Section, can be a compositeof material having first and second layers, in which the first or innerlayer 288 interfaces with the elastomeric stopper 282 and is effectiveto reduce the transmission of one or more constituents of the stopper282 into the vessel lumen. The second layer 286 can interface with theinner wall 280 of the vessel and is effective as a lubricity layer toreduce friction between the stopper 282 and the inner wall 280 of thevessel when the stopper 282 is seated on or in the vessel 268. Suchcomposites are described in connection with syringe coatings elsewherein this specification.

VII.A.2.a. Or, the first and second layers 288 and 286 are defined by acoating of graduated properties, in which the values of y and z definedin the Definition Section are greater in the first layer than in thesecond layer.

VII.A.2.a. The lubricity and/or hydrophobic layer can be applied, forexample, by PECVD substantially as previously described. The lubricityand/or hydrophobic layer can be, for example, between 0.5 and 5000 nm (5to 50,000 Angstroms) thick, or between 1 and 5000 nm thick, or between 5and 5000 nm thick, or between 10 and 5000 nm thick, or between 20 and5000 nm thick, or between 50 and 5000 nm thick, or between 100 and 5000nm thick, or between 200 and 5000 nm thick, or between 500 and 5000 nmthick, or between 1000 and 5000 nm thick, or between 2000 and 5000 nmthick, or between 3000 and 5000 nm thick, or between 4000 and 10,000 nmthick.

VII.A.2.a. Certain advantages are contemplated for plasma coatedlubricity layers, versus the much thicker (one micron or greater)conventional spray applied silicone lubricants. Plasma coatings have amuch lower migratory potential to move into blood versus sprayed ormicron-coated silicones, both because the amount of plasma coatedmaterial is much less and because it can be more intimately applied tothe coated contact surface and better bonded in place.

VII.A.2.a. Nanocoatings, as applied by PECVD, are contemplated to offerlower resistance to sliding of an adjacent contact surface or flow of anadjacent fluid than micron coatings, as the plasma coating tends toprovide a smoother contact surface.

VII.A.2.a. Still another embodiment is a method of applying a coating ofa lubricity and/or hydrophobic layer on an elastomeric stopper. Thestopper can be used, for example, to close the vessel previouslydescribed. The method includes several parts. A stopper is placed in asubstantially evacuated chamber. A reaction mixture is providedcomprising plasma forming gas, i.e. an organosilicon compound gas,optionally an oxidizing gas, and optionally a hydrocarbon gas. Plasma isformed in the reaction mixture. The stopper is contacted with thereaction mixture, depositing the coating of a lubricity and/orhydrophobic layer on at least a portion of the stopper.

VII.A.2.a. In practicing this method, to obtain higher values of y and zas defined in the Definition Section, it is contemplated that thereaction mixture can comprise a hydrocarbon gas, as further describedabove and below. Optionally, the reaction mixture can contain oxygen, iflower values of y and z or higher values of x are contemplated. Or,particularly to reduce oxidation and increase the values of y and z, thereaction mixture can be essentially free of an oxidizing gas.

VII.A.2.a. In practicing this method to coat certain embodiments of thestopper such as the stopper 282, it is contemplated to be unnecessary toproject the reaction mixture into the concavities of the stopper. Forexample, the wall-contacting and interior facing contact surfaces 276and 272 of the stopper 282 are essentially convex, and thus readilytreated by a batch process in which a multiplicity of stoppers such as282 can be located and treated in a single substantially evacuatedreaction chamber. It is further contemplated that in some embodimentsthe coatings 286 and 288 do not need to present as formidable a barrierto oxygen or water as the barrier coating on the interior contactsurface 280 of the vessel 268, as the material of the stopper 282 canserve this function to a large degree.

VII.A.2.a. Many variations of the stopper and the stopper coatingprocess are contemplated. The stopper 282 can be contacted with theplasma. Or, the plasma can be formed upstream of the stopper 282,producing plasma product, and the plasma product can be contacted withthe stopper 282. The plasma can be formed by exciting the reactionmixture with electromagnetic energy and/or microwave energy.

VII.A.2.a. Variations of the reaction mixture are contemplated. Theplasma forming gas can include an inert gas. The inert gas can be, forexample, argon or helium, or other gases described in this disclosure.The organosilicon compound gas can be, or include, HMDSO, OMCTS, any ofthe other organosilicon compounds mentioned in this disclosure, or acombination of two or more of these. The oxidizing gas can be oxygen orthe other gases mentioned in this disclosure, or a combination of two ormore of these. The hydrocarbon gas can be, for example, methane,methanol, ethane, ethylene, ethanol, propane, propylene, propanol,acetylene, or a combination of two or more of these.

VII.A.2.b. Applying by PECVD a Coating of Group III or IV Element andCarbon on a Stopper

VII.A.2.b. Another embodiment is a method of applying a coating of acomposition including carbon and one or more elements of Groups III orIV on an elastomeric stopper. To carry out the method, a stopper islocated in a deposition chamber.

VII.A.2.b. A reaction mixture is provided in the deposition chamber,including a plasma forming gas with a gaseous source of a Group IIIelement, a Group IV element, or a combination of two or more of these.The reaction mixture optionally contains an oxidizing gas and optionallycontains a gaseous compound having one or more C—H bonds. Plasma isformed in the reaction mixture, and the stopper is contacted with thereaction mixture. A coating of a Group III element or compound, a GroupIV element or compound, or a combination of two or more of these isdeposited on at least a portion of the stopper.

VII.A.3. Stoppered Plastic Vessel Having Barrier Coating Effective toProvide 95% Vacuum Retention for 24 Months

VII.A.3. Another embodiment is a vessel including a vessel, a barriercoating, and a closure. The vessel is generally tubular and made ofthermoplastic material. The vessel has a mouth and a lumen bounded atleast in part by a wall. The wall has an inner contact surfaceinterfacing with the lumen. An at least essentially continuous barriercoating is applied on the inner contact surface of the wall. The barriercoating is effective to provide a substantial shelf life. A closure isprovided covering the mouth of the vessel and isolating the lumen of thevessel from ambient air.

VII.A.3. Referring to FIGS. 3-5, a vessel 268 such as an evacuated bloodcollection tube or other vessel is shown.

VII.A.3. The vessel is, in this embodiment, a generally tubular vesselhaving an at least essentially continuous barrier coating and a closure.The vessel is made of thermoplastic material having a mouth and a lumenbounded at least in part by a wall having an inner contact surfaceinterfacing with the lumen. The barrier coating is deposited on theinner contact surface of the wall, and is effective to maintain at least95%, or at least 90%, of the initial vacuum level of the vessel for ashelf life of at least 24 months, optionally at least 30 months,optionally at least 36 months. The closure covers the mouth of thevessel and isolates the lumen of the vessel from ambient air.

VII.A.3. The closure, for example the closure 270 illustrated in theFigures or another type of closure, is provided to maintain a partialvacuum and/or to contain a sample and limit or prevent its exposure tooxygen or contaminants. FIGS. 3-5 are based on figures found in U.S.Pat. No. 6,602,206, but the present discovery is not limited to that orany other particular type of closure.

VII.A.3. The closure 270 comprises a interior-facing contact surface 272exposed to the lumen 274 of the vessel 268 and a wall-contacting contactsurface 276 that is in contact with the inner contact surface 278 of thevessel wall 280. In the illustrated embodiment the closure 270 is anassembly of a stopper 282 and a shield 284.

VII.A.3. In the illustrated embodiment, the stopper 282 defines thewall-contacting contact surface 276 and the inner contact surface 278,while the shield is largely or entirely outside the stoppered vessel268, retains and provides a grip for the stopper 282, and shields aperson removing the closure 270 from being exposed to any contentsexpelled from the vessel 268, such as due to a pressure differenceinside and outside of the vessel 268 when the vessel 268 is opened andair rushes in or out to equalize the pressure difference.

VII.A.3. It is further contemplated that the coatings on the vessel wall280 and the wall contacting contact surface 276 of the stopper can becoordinated. The stopper can be coated with a lubricity silicone layer,and the vessel wall 280, made for example of PET or glass, can be coatedwith a harder SiO_(x) layer, or with an underlying SiO_(x) layer and alubricity overcoat.

VII.B. Syringes

VII.B. The foregoing description has largely addressed applying abarrier coating to a tube with one permanently closed end, such as ablood collection tube or, more generally, a specimen receiving tube 80.The apparatus is not limited to such a device.

VII.B. Another example of a suitable vessel, shown in FIG. 2, is asyringe barrel 250 for a medical syringe 252. Such syringes 252 aresometimes supplied prefilled with saline solution, a pharmaceuticalpreparation, or the like for use in medical techniques. Pre-filledsyringes 252 are also contemplated to benefit from an SiO_(x) barrier orother type of coating on the interior contact surface 254 to keep thecontents of the prefilled syringe 252 out of contact with the plastic ofthe syringe, for example of the syringe barrel 250 during storage. Thebarrier or other type of coating can be used to avoid leachingcomponents of the plastic into the contents of the barrel through theinterior contact surface 254.

VII.B. A syringe barrel 250 as molded commonly can be open at both theback end 256, to receive a plunger 258, and at the front end 260, toreceive a hypodermic needle, a nozzle, or tubing for dispensing thecontents of the syringe 252 or for receiving material into the syringe252. But the front end 260 can optionally be capped and the plunger 258optionally can be fitted in place before the prefilled syringe 252 isused, closing the barrel 250 at both ends. A cap 262 can be installedeither for the purpose of processing the syringe barrel 250 or assembledsyringe, or to remain in place during storage of the prefilled syringe252, up to the time the cap 262 is removed and (optionally) a hypodermicneedle or other delivery conduit is fitted on the front end 260 toprepare the syringe 252 for use.

VII.B.1.a. Syringe Having Barrel Coated with Lubricity Layer Depositedfrom an Organosilicon Precursor

VII.B.1.a. Still another embodiment is a vessel having a lubricitylayer, characterized as defined in the Definition Section, of the typemade by the following process.

VII.B.1.a. A precursor is provided as defined above.

VII.B.1.a. The precursor is applied to a substrate under conditionseffective to form a coating. The coating is polymerized or crosslinked,or both, to form a lubricated contact surface having a lower plungersliding force or breakout force than the untreated substrate.

VII.B.1.a. Respecting any of the Embodiments VII and sub-parts,optionally the applying step is carried out by vaporizing the precursorand providing it in the vicinity of the substrate.

VII.B.1.a. Respecting any of the Embodiments VII.A.1.a.i, optionally aplasma, optionally a non-hollow-cathode plasma, is formed in thevicinity of the substrate. Optionally, the precursor is provided in thesubstantial absence of oxygen. Optionally, the precursor is provided inthe substantial absence of a carrier gas. Optionally, the precursor isprovided in the substantial absence of nitrogen. Optionally, theprecursor is provided at less than 1 Torr absolute pressure. Optionally,the precursor is provided to the vicinity of a plasma emission.Optionally, the precursor its reaction product is applied to thesubstrate at a thickness of 1 to 5000 nm thick, or 10 to 1000 nm thick,or 10-200 nm thick, or 20 to 100 nm thick. Optionally, the substratecomprises glass. Optionally, the substrate comprises a polymer,optionally a polycarbonate polymer, optionally an olefin polymer,optionally a cyclic olefin copolymer, optionally a polypropylenepolymer, optionally a polyester polymer, optionally a polyethyleneterephthalate polymer.

VII.B.1.a. Optionally, the plasma is generated by energizing the gaseousreactant containing the precursor with electrodes powered, for example,at a RF frequency as defined above, for example a frequency of from 10kHz to less than 300 MHz, optionally from 1 to 50 MHz, even optionallyfrom 10 to 15 MHz, optionally a frequency of 13.56 MHz.

VII.B.1.a. Optionally, the plasma is generated by energizing the gaseousreactant containing the precursor with electrodes supplied with anelectric power of from 0.1 to 25 W, optionally from 1 to 22 W,optionally from 3 to 17 W, even optionally from 5 to 14 W, optionallyfrom 7 to 11 W, optionally 8 W. The ratio of the electrode power to theplasma volume can be less than 10 W/ml, optionally is from 5 W/ml to 0.1W/ml, optionally is from 4 W/ml to 0.1 W/ml, optionally is from 2 W/mlto 0.2 W/ml. These power levels are suitable for applying lubricitylayers to syringes and sample tubes and vessels of similar geometryhaving a void volume of 1 to 3 mL in which PECVD plasma is generated. Itis contemplated that for larger or smaller objects the power appliedshould be increased or reduced accordingly to scale the process to thesize of the substrate.

VII.B.1.a. Another embodiment is a lubricity layer, characterized asdefined in the Definition Section, on the inner wall of a syringebarrel. The coating is produced from a PECVD process using the followingmaterials and conditions. A cyclic precursor is optionally employed,selected from a monocyclic siloxane, a polycyclic siloxane, or acombination of two or more of these, as defined elsewhere in thisspecification for lubricity layers. One example of a suitable cyclicprecursor comprises octamethylcyclotetrasiloxane (OMCTS), optionallymixed with other precursor materials in any proportion. Optionally, thecyclic precursor consists essentially of octamethylcyclotetrasiloxane(OMCTS), meaning that other precursors can be present in amounts whichdo not change the basic and novel properties of the resulting lubricitylayer, i.e. its reduction of the plunger sliding force or breakout forceof the coated contact surface.

VII.B.1.a. At least essentially no oxygen as defined in the DefinitionSection is added to the process.

VII.B.1.a. A sufficient plasma generation power input, for example anypower level successfully used in one or more working examples of thisspecification or described in the specification, is provided to inducecoating formation.

VII.B.1.a. The materials and conditions employed are effective to reducethe syringe plunger sliding force or breakout force moving through thesyringe barrel at least 25 percent, alternatively at least 45 percent,alternatively at least 60 percent, alternatively greater than 60percent, relative to an uncoated syringe barrel. Ranges of plungersliding force or breakout force reduction of from 20 to 95 percent,alternatively from 30 to 80 percent, alternatively from 40 to 75percent, alternatively from 60 to 70 percent, are contemplated.

VII.B.1.a. Another embodiment is a vessel having a hydrophobic layer,characterized as defined in the Definition Section, on the inside wall.The coating is made as explained for the lubricant coating of similarcomposition, but under conditions effective to form a hydrophobiccontact surface having a higher contact angle than the untreatedsubstrate.

VII.B.1.a. Respecting any of the Embodiments VII.A.1.a.ii, optionallythe substrate comprises glass or a polymer. The glass optionally isborosilicate glass. The polymer is optionally a polycarbonate polymer,optionally an olefin polymer, optionally a cyclic olefin copolymer,optionally a polypropylene polymer, optionally a polyester polymer,optionally a polyethylene terephthalate polymer.

VII.B.1.a. Another embodiment is a syringe including a plunger, asyringe barrel, and a lubricity layer, characterized as defined in theDefinition Section. The syringe barrel includes an interior contactsurface receiving the plunger for sliding. The lubricity layer isdisposed on the interior contact surface of the syringe barrel. Thelubricity layer is less than 1000 nm thick and effective to reduce thebreakout force or the plunger sliding force necessary to move theplunger within the barrel. Reducing the plunger sliding force isalternatively expressed as reducing the coefficient of sliding frictionof the plunger within the barrel or reducing the plunger force; theseterms are regarded as having the same meaning in this specification.

VII.B.1.a. Any of the above precursors of any type can be used alone orin combinations of two or more of them to provide a lubricity layer.

VII.B.1.a. In addition to utilizing vacuum processes, low temperatureatmospheric (non-vacuum) plasma processes can also be utilized to inducemolecular ionization and deposition through precursor monomer vapordelivery optionally in a non-oxidizing atmosphere such as helium orargon. Separately, thermal CVD can be considered via flash thermolysisdeposition.

VII.B.1.a. The approaches above are similar to vacuum PECVD in that thecontact surface coating and crosslinking mechanisms can occursimultaneously.

VII.B.1.a. Yet another expedient contemplated for any coating orcoatings described here is a coating that is not uniformly applied overthe entire interior 88 of a vessel. For example, a different oradditional coating can be applied selectively to the cylindrical portionof the vessel interior, compared to the hemispherical portion of thevessel interior at its closed end 84, or vice versa. This expedient isparticularly contemplated for a syringe barrel or a sample collectiontube as described below, in which a lubricity layer might be provided onpart or all of the cylindrical portion of the barrel, where the plungeror piston or closure slides, and not elsewhere.

VII.B.1.a. Optionally, the precursor can be provided in the presence,substantial absence, or absence of oxygen, in the presence, substantialabsence, or absence of nitrogen, or in the presence, substantialabsence, or absence of a carrier gas. In one contemplated embodiment,the precursor alone is delivered to the substrate and subjected to PECVDto apply and cure the coating.

VII.B.1.a. Optionally, the precursor can be provided at less than 1 Torrabsolute pressure.

VII.B.1.a. Optionally, the precursor can be provided to the vicinity ofa plasma emission.

VII.B.1.a. Optionally, the precursor its reaction product can be appliedto the substrate at a thickness of 1 to 5000 nm, or 10 to 1000 nm., or10-200 nm, or 20 to 100 nm.

VII.B.1.a. In any of the above embodiments, the substrate can compriseglass, or a polymer, for example one or more of a polycarbonate polymer,an olefin polymer (for example a cyclic olefin copolymer or apolypropylene polymer), or a polyester polymer (for example, apolyethylene terephthalate polymer).

VII.B.1.a. In any of the above embodiments, the plasma is generated byenergizing the gaseous reactant containing the precursor with electrodespowered at a RF frequency as defined in this description.

VII.B.1.a. In any of the above embodiments, the plasma is generated byenergizing the gaseous reactant containing the precursor with electrodessupplied with sufficient electric power to generate a lubricity layer.Optionally, the plasma is generated by energizing the gaseous reactantcontaining the precursor with electrodes supplied with an electric powerof from 0.1 to 25 W, optionally from 1 to 22 W, optionally from 3 to 17W, even optionally from 5 to 14 W, optionally from 7 to 11 W, optionally8 W. The ratio of the electrode power to the plasma volume can be lessthan 10 W/ml, optionally is from 5 W/ml to 0.1 W/ml, optionally is from4 W/ml to 0.1 W/ml, optionally from 2 W/ml to 0.2 W/ml. These powerlevels are suitable for applying lubricity layers to syringes and sampletubes and vessels of similar geometry having a void volume of 1 to 3 mLin which PECVD plasma is generated. It is contemplated that for largeror smaller objects the power applied should be increased or reducedaccordingly to scale the process to the size of the substrate.

VII.B.1.a. The coating can be cured, as by polymerizing or crosslinkingthe coating, or both, to form a lubricated contact surface having alower plunger sliding force or breakout force than the untreatedsubstrate. Curing can occur during the application process such asPECVD, or can be carried out or at least completed by separateprocessing.

VII.B.1.a. Although plasma deposition has been used herein todemonstrate the coating characteristics, alternate deposition methodscan be used as long as the chemical composition of the starting materialis preserved as much as possible while still depositing a solid filmthat is adhered to the base substrate.

VII.B.1.a. For example, the coating material can be applied onto thesyringe barrel (from the liquid state) by spraying the coating ordipping the substrate into the coating, where the coating is either theneat precursor a solvent-diluted precursor (allowing the mechanicaldeposition of a thinner coating). The coating optionally can becrosslinked using thermal energy, UV energy, electron beam energy,plasma energy, or any combination of these.

VII.B.1.a. Application of a silicone precursor as described above onto acontact surface followed by a separate curing step is also contemplated.The conditions of application and curing can be analogous to those usedfor the atmospheric plasma curing of pre-coated polyfluoroalkyl ethers,a process practiced under the trademark TriboGlide®. More details ofthis process can be found at http://www.triboglide.com/process.htm.

VII.B.1.a. In such a process, the area of the part to be coated canoptionally be pre-treated with an atmospheric plasma. This pretreatmentcleans and activates the contact surface so that it is receptive to thelubricant that is sprayed in the next step.

VII.B.1.a. The lubrication fluid, in this case one of the aboveprecursors or a polymerized precursor, is then sprayed on to the contactsurface to be treated. For example, IVEK precision dispensing technologycan be used to accurately atomize the fluid and create a uniformcoating.

VII.B.1.a. The coating is then bonded or crosslinked to the part, againusing an atmospheric plasma field. This both immobilizes the coating andimproves the lubricant's performance.

VII.B.1.a. Optionally, the atmospheric plasma can be generated fromambient air in the vessel, in which case no gas feed and no vacuumdrawing equipment is needed. Optionally, however, the vessel is at leastsubstantially closed while plasma is generated, to minimize the powerrequirement and prevent contact of the plasma with contact surfaces ormaterials outside the vessel.

VII.B.1.a.i. Lubricity Layer: SiO_(x) Barrier, Lubricity Layer, ContactSurface Treatment

Contact Surface Treatment

VII.B.1.a.i. Another embodiment is a syringe comprising a barreldefining a lumen and having an interior contact surface slidablyreceiving a plunger, i.e. receiving a plunger for sliding contact to theinterior contact surface.

VII.B.1.a.i. The syringe barrel is made of thermoplastic base material.

VII.B.1.a.i. Optionally, the interior contact surface of the barrel iscoated with an SiO_(x) barrier layer as described elsewhere in thisspecification.

VII.B.1.a.i. A lubricity layer is applied to the barrel interior contactsurface, the plunger, or both, or to the previously applied SiO_(x)barrier layer. The lubricity layer can be provided, applied, and curedas set out in embodiment VII.B.1.a or elsewhere in this specification.

VII.B.1.a.i. For example, the lubricity layer can be applied, in anyembodiment, by PECVD. The lubricity layer is deposited from anorganosilicon precursor, and is less than 1000 nm thick.

VII.B.1.a.i. A contact surface treatment is carried out on the lubricitylayer in an amount effective to reduce the leaching or extractables ofthe lubricity layer, the thermoplastic base material, or both. Thetreated contact surface can thus act as a solute retainer. This contactsurface treatment can result in a skin coating, e.g. a skin coatingwhich is at least 1 nm thick and less than 100 nm thick, or less than 50nm thick, or less than 40 nm thick, or less than 30 nm thick, or lessthan 20 nm thick, or less than 10 nm thick, or less than 5 nm thick, orless than 3 nm thick, or less than 2 nm thick, or less than 1 nm thick,or less than 0.5 nm thick.

VII.B.1.a.i. As used herein, “leaching” refers to material transferredout of a substrate, such as a vessel wall, into the contents of avessel, for example a syringe. Commonly, leachables are measured bystoring the vessel filled with intended contents, then analyzing thecontents to determine what material leached from the vessel wall intothe intended contents. “Extraction” refers to material removed from asubstrate by introducing a solvent or dispersion medium other than theintended contents of the vessel, to determine what material can beremoved from the substrate into the extraction medium under theconditions of the test.

VII.B.1.a.i. The contact surface treatment resulting in a soluteretainer optionally can be a SiO_(x) layer as previously defined in thisspecification or a hydrophobic layer, characterized as defined in theDefinition Section. In one embodiment, the contact surface treatment canbe applied by PECVD deposit of SiO_(x) or a hydrophobic layer.Optionally, the contact surface treatment can be applied using higherpower or stronger oxidation conditions than used for creating thelubricity layer, or both, thus providing a harder, thinner, continuoussolute retainer 539. Contact surface treatment can be less than 100 nmdeep, optionally less than 50 nm deep, optionally less than 40 nm deep,optionally less than 30 nm deep, optionally less than 20 nm deep,optionally less than 10 nm deep, optionally less than 5 nm deep,optionally less than 3 nm deep, optionally less than 1 nm deep,optionally less than 0.5 nm deep, optionally between 0.1 and 50 nm deepin the lubricity layer.

VII.B.1.a.i. The solute retainer is contemplated to provide low soluteleaching performance to the underlying lubricity and other layers,including the substrate, as required. This retainer would only need tobe a solute retainer to large solute molecules and oligomers (forexample siloxane monomers such as HMDSO, OMCTS, their fragments andmobile oligomers derived from lubricants, for example a “leachablesretainer”) and not a gas (O₂/N₂/CO₂/water vapor) barrier layer. A soluteretainer can, however, also be a gas barrier (e.g. the SiO_(x) coatingaccording to present invention. One can create a good leachable retainerwithout gas barrier performance, either by vacuum or atmospheric-basedPECVD processes. It is desirable that the “leachables barrier” will besufficiently thin that, upon syringe plunger movement, the plunger willreadily penetrate the “solute retainer” exposing the sliding plungernipple to the lubricity layer immediately below to form a lubricatedcontact surface having a lower plunger sliding force or breakout forcethan the untreated substrate.

VII.B.1.a.i. In another embodiment, the contact surface treatment can beperformed by oxidizing the contact surface of a previously appliedlubricity layer, as by exposing the contact surface to oxygen in aplasma environment. The plasma environment described in thisspecification for forming SiO_(x) coatings can be used. Or, atmosphericplasma conditions can be employed in an oxygen-rich environment.

VII.B.1.a.i. The lubricity layer and solute retainer, however formed,optionally can be cured at the same time. In another embodiment, thelubricity layer can be at least partially cured, optionally fully cured,after which the contact surface treatment can be provided, applied, andthe solute retainer can be cured.

VII.B.1.a.i. The lubricity layer and solute retainer are composed, andpresent in relative amounts, effective to provide a breakout force,plunger sliding force, or both that is less than the corresponding forcerequired in the absence of the lubricity layer and contact surfacetreatment. In other words, the thickness and composition of the soluteretainer are such as to reduce the leaching of material from thelubricity layer into the contents of the syringe, while allowing theunderlying lubricity layer to lubricate the plunger. It is contemplatedthat the solute retainer will break away easily and be thin enough thatthe lubricity layer will still function to lubricate the plunger when itis moved.

VII.B.1.a.i. In one contemplated embodiment, the lubricity and contactsurface treatments can be applied on the barrel interior contactsurface. In another contemplated embodiment, the lubricity and contactsurface treatments can be applied on the plunger. In still anothercontemplated embodiment, the lubricity and contact surface treatmentscan be applied both on the barrel interior contact surface and on theplunger. In any of these embodiments, the optional SiO_(x) barrier layeron the interior of the syringe barrel can either be present or absent.

VII.B.1.a.i. One embodiment contemplated is a plural-layer, e.g. a3-layer, configuration applied to the inside contact surface of asyringe barrel. Layer 1 can be an SiO_(x) gas barrier made by PECVD ofHMDSO, OMCTS, or both, in an oxidizing atmosphere. Such an atmospherecan be provided, for example, by feeding HMDSO and oxygen gas to a PECVDcoating apparatus as described in this specification. Layer 2 can be alubricity layer using OMCTS applied in a non-oxidizing atmosphere. Sucha non-oxidizing atmosphere can be provided, for example, by feedingOMCTS to a PECVD coating apparatus as described in this specification,optionally in the substantial or complete absence of oxygen. Asubsequent solute retainer can be formed by a treatment forming a thinskin layer of SiO_(x) or a hydrophobic layer as a solute retainer usinghigher power and oxygen using OMCTS and/or HMDSO.

VII.B.1.a.i. Certain of these plural-layer coatings are contemplated tohave one or more of the following optional advantages, at least to somedegree. They can address the reported difficulty of handling silicone,since the solute retainer can confine the interior silicone and preventit from migrating into the contents of the syringe or elsewhere,resulting in fewer silicone particles in the deliverable contents of thesyringe and less opportunity for interaction between the lubricity layerand the contents of the syringe. They can also address the issue ofmigration of the lubricity layer away from the point of lubrication,improving the lubricity of the interface between the syringe barrel andthe plunger. For example, the break-free force can be reduced and thedrag on the moving plunger can be reduced, or optionally both.

VII.B.1.a.i. It is contemplated that when the solute retainer is broken,the solute retainer will continue to adhere to the lubricity layer andthe syringe barrel, which can inhibit any particles from being entrainedin the deliverable contents of the syringe.

VII.B.1.a.i. Certain of these coatings will also provide manufacturingadvantages, particularly if the barrier coating, lubricity layer andcontact surface treatment are applied in the same apparatus, for examplethe illustrated PECVD apparatus. Optionally, the SiO_(x) barriercoating, lubricity layer, and contact surface treatment can all beapplied in one PECVD apparatus, thus greatly reducing the amount ofhandling necessary.

Further advantages can be obtained by forming the barrier coating,lubricity layer, and solute retainer using the same precursors andvarying the process. For example, an SiO_(x) gas barrier layer can beapplied using an OMCTS precursor under high power/high O₂ conditions,followed by applying a lubricity layer applied using an OMCTS precursorunder low power and/or in the substantial or complete absence of oxygen,finishing with a contact surface treatment using an OMCTS precursorunder intermediate power and oxygen.

VII.B.1.b Syringe Having Barrel with SiO_(x) Coated Interior and BarrierCoated Exterior

VII.B.1.b. In any embodiment, the thermoplastic base material optionallycan include a polyolefin, for example polypropylene or a cyclic olefincopolymer (for example the material sold under the trademark TOPAS®), apolyester, for example polyethylene terephthalate, a polycarbonate, forexample a bisphenol A polycarbonate thermoplastic, or other materials.Composite syringe barrels are contemplated having any one of thesematerials as an outer layer and the same or a different one of thesematerials as an inner layer. Any of the material combinations of thecomposite syringe barrels or sample tubes described elsewhere in thisspecification can also be used.

VII.B.1.b. In any embodiment, the resin optionally can includepolyvinylidene chloride in homopolymer or copolymer form. For example,the PVdC homopolymers (trivial name: Saran) or copolymers described inU.S. Pat. No. 6,165,566, incorporated here by reference, can beemployed. The resin optionally can be applied onto the exterior contactsurface of the barrel in the form of a latex or other dispersion.

VII.B.1.b. In any embodiment, the syringe barrel 548 optionally caninclude a lubricity layer disposed between the plunger and the barriercoating of SiO_(x). Suitable lubricity layers are described elsewhere inthis specification.

VII.B.1.b. In any embodiment, the lubricity layer optionally can beapplied by PECVD and optionally can include material characterized asdefined in the Definition Section.

VII.B.1.b. In any embodiment, the syringe barrel 548 optionally caninclude a contact surface treatment covering the lubricity layer in anamount effective to reduce the leaching of the lubricity layer,constituents of the thermoplastic base material, or both into the lumen604.

VII.B.1.c Method of Making Syringe Having Barrel with SiO_(x) CoatedInterior and Barrier Coated Exterior

VII.B.1.c. Even another embodiment is a method of making a syringe asdescribed in any of the embodiments of part VII.B.1.b, including aplunger, a barrel, and interior and exterior barrier coatings. A barrelis provided having an interior contact surface for receiving the plungerfor sliding and an exterior contact surface. A barrier coating ofSiO_(x) is provided on the interior contact surface of the barrel byPECVD. A barrier coating of a resin is provided on the exterior contactsurface of the barrel. The plunger and barrel are assembled to provide asyringe.

VII.B.1.c. For effective coating (uniform wetting) of the plasticarticle with the aqueous latex, it is contemplated to be useful to matchthe contact surface tension of the latex to the plastic substrate. Thiscan be accomplished by several approaches, independently or combined,for example, reducing the contact surface tension of the latex (withsurfactants or solvents), and/or corona pretreatment of the plasticarticle, and/or chemical priming of the plastic article.

VII.B.1.c. The resin optionally can be applied via dip coating of thelatex onto the exterior contact surface of the barrel, spray coating ofthe latex onto the exterior contact surface of the barrel, or both,providing plastic-based articles offering improved gas and vapor barrierperformance. Polyvinylidene chloride plastic laminate articles can bemade that provide significantly improved gas barrier performance versusthe non-laminated plastic article.

VII.B.1.c. In any embodiment, the resin optionally can be heat cured.The resin optionally can be cured by removing water. Water can beremoved by heat curing the resin, exposing the resin to a partial vacuumor low-humidity environment, catalytically curing the resin, or otherexpedients.

VII.B.1.c. An effective thermal cure schedule is contemplated to providefinal drying to permit PVdC crystallization, offering barrierperformance. Primary curing can be carried out at an elevatedtemperature, for example between 180-310° F. (82-154° C.), of coursedepending on the heat tolerance of the thermoplastic base material.Barrier performance after the primary cure optionally can be about 85%of the ultimate barrier performance achieved after a final cure.

VII.B.1.c. A final cure can be carried out at temperatures ranging fromambient temperature, such as about 65-75° F. (18-24° C.) for a long time(such as 2 weeks) to an elevated temperature, such as 122° F. (50° C.),for a short time, such as four hours.

VII.B.1.c. The PVdC-plastic laminate articles, in addition to superiorbarrier performance, are optionally contemplated to provide one or moredesirable properties such as colorless transparency, good gloss,abrasion resistance, printability, and mechanical strain resistance.

VII.B.2. Plungers

VII.B.2.a. With Barrier Coated Piston Front Face

VII.B.2.a. Another embodiment is a plunger for a syringe, including apiston and a push rod. The piston has a front face, a generallycylindrical side face, and a back portion, the side face beingconfigured to movably seat within a syringe barrel. The front face has abarrier coating. The push rod engages the back portion and is configuredfor advancing the piston in a syringe barrel.

VII.B.2.b. With Lubricity Layer Interfacing with Side Face

VII.B.2.b. Yet another embodiment is a plunger for a syringe, includinga piston, a lubricity layer, and a push rod. The piston has a frontface, a generally cylindrical side face, and a back portion. The sideface is configured to movably seat within a syringe barrel. Thelubricity layer interfaces with the side face. The push rod engages theback portion of the piston and is configured for advancing the piston ina syringe barrel.

VII.B.3. Two Piece Syringe and Luer Fitting

VII.B.3. Another embodiment is a syringe including a plunger, a syringebarrel, and a Luer fitting. The syringe includes a barrel having aninterior contact surface receiving the plunger for sliding. The Luerfitting includes a Luer taper having an internal passage defined by aninternal contact surface. The Luer fitting is formed as a separate piecefrom the syringe barrel and joined to the syringe barrel by a coupling.The internal passage of the Luer taper has a barrier coating of SiO_(x).

VII.B.4. Lubricant Compositions—Lubricity Layer Deposited from anOrganosilicon Precursor Made by In Situ Polymerizing OrganosiliconPrecursorVII.B.4.a. Product by Process and Lubricity

VII.B.4.a. Still another embodiment is a lubricity layer. This coatingcan be of the type made by the following process.

VII.B.4.a. Any of the precursors mentioned elsewhere in thisspecification can be used, alone or in combination. The precursor isapplied to a substrate under conditions effective to form a coating. Thecoating is polymerized or crosslinked, or both, to form a lubricatedcontact surface having a lower plunger sliding force or breakout forcethan the untreated substrate.

VII.B.4.a. Another embodiment is a method of applying a lubricity layer.An organosilicon precursor is applied to a substrate under conditionseffective to form a coating. The coating is polymerized or crosslinked,or both, to form a lubricated contact surface having a lower plungersliding force or breakout force than the untreated substrate.

VII.B.4.b. Product by Process and Analytical Properties

VII.B.4.b. Even another aspect of the invention is a lubricity layerdeposited by PECVD from a feed gas comprising an organometallicprecursor, optionally an organosilicon precursor, optionally a linearsiloxane, a linear silazane, a monocyclic siloxane, a monocyclicsilazane, a polycyclic siloxane, a polycyclic silazane, or anycombination of two or more of these. The coating has a density between1.25 and 1.65 g/cm³ optionally between 1.35 and 1.55 g/cm³, optionallybetween 1.4 and 1.5 g/cm³, optionally between 1.44 and 1.48 g/cm³ asdetermined by X-ray reflectivity (XRR).

VII.B.4.b. Still another aspect of the invention is a lubricity layerdeposited by PECVD from a feed gas comprising an organometallicprecursor, optionally an organosilicon precursor, optionally a linearsiloxane, a linear silazane, a monocyclic siloxane, a monocyclicsilazane, a polycyclic siloxane, a polycyclic silazane, or anycombination of two or more of these. The coating has as an outgascomponent one or more oligomers containing repeating -(Me)₂SiO—moieties, as determined by gas chromatography/mass spectrometry.Optionally, the coating meets the limitations of any of embodimentsVII.B.4.a or VII.B.4.b.A.585h. Optionally, the coating outgas componentas determined by gas chromatography/mass spectrometry is substantiallyfree of trimethylsilanol.

VII.B.4.b. Optionally, the coating outgas component can be at least 10ng/test of oligomers containing repeating -(Me)₂SiO— moieties, asdetermined by gas chromatography/mass spectrometry using the followingtest conditions:

-   -   GC Column: 30 m×0.25 mm DB-5MS (J&W Scientific), 0.25 μm film        thickness    -   Flow rate: 1.0 ml/min, constant flow mode    -   Detector: Mass Selective Detector (MSD)    -   Injection Mode: Split injection (10:1 split ratio)    -   Outgassing Conditions: 1½″ (37 mm) Chamber, purge for three hour        at 85° C., flow 60 ml/min    -   Oven temperature: 40° C. (5 min.) to 300° C. at 10° C./min.;        hold for 5 min. at 300° C.

VII.B.4.b. Optionally, the outgas component can include at least 20ng/test of oligomers containing repeating -(Me)₂SiO— moieties.

VII.B.4.b. Optionally, the feed gas comprises a monocyclic siloxane, amonocyclic silazane, a polycyclic siloxane, a polycyclic silazane, orany combination of two or more of these, for example a monocyclicsiloxane, a monocyclic silazane, or any combination of two or more ofthese, for example octamethylcyclotetrasiloxane.

VII.B.4.b. The lubricity layer of any embodiment can have a thicknessmeasured by transmission electron microscopy (TEM) between 1 and 500 nm,optionally between 10 and 500 nm, optionally between 20 and 200 nm,optionally between 20 and 100 nm, optionally between 30 and 100 nm.

VII.B.4.b. Another aspect of the invention is a lubricity layerdeposited by PECVD from a feed gas comprising a monocyclic siloxane, amonocyclic silazane, a polycyclic siloxane, a polycyclic silazane, orany combination of two or more of these. The coating has an atomicconcentration of carbon, normalized to 100% of carbon, oxygen, andsilicon, as determined by X-ray photoelectron spectroscopy (XPS),greater than the atomic concentration of carbon in the atomic formulafor the feed gas. Optionally, the coating meets the limitations ofembodiments VII.B.4.a or VII.B.4.b.A.

VII.B.4.b. Optionally, the atomic concentration of carbon increases byfrom 1 to 80 atomic percent (as calculated and based on the XPSconditions in Example 13), alternatively from 10 to 70 atomic percent,alternatively from 20 to 60 atomic percent, alternatively from 30 to 50atomic percent, alternatively from 35 to 45 atomic percent,alternatively from 37 to 41 atomic percent.

VII.B.4.b. An additional aspect of the invention is a lubricity layerdeposited by PECVD from a feed gas comprising a monocyclic siloxane, amonocyclic silazane, a polycyclic siloxane, a polycyclic silazane, orany combination of two or more of these. The coating has an atomicconcentration of silicon, normalized to 100% of carbon, oxygen, andsilicon, as determined by X-ray photoelectron spectroscopy (XPS), lessthan the atomic concentration of silicon in the atomic formula for thefeed gas. Optionally, the coating meets the limitations of embodimentsVII.B.4.a or VII.B.4.b.A.

VII.B.4.b. Optionally, the atomic concentration of silicon decreases byfrom 1 to 80 atomic percent (as calculated and based on the XPSconditions in Example 13), alternatively from 10 to 70 atomic percent,alternatively from 20 to 60 atomic percent, alternatively from 30 to 55atomic percent, alternatively from 40 to 50 atomic percent,alternatively from 42 to 46 atomic percent.

VII.B.4.b. Lubricity layers having combinations of any two or moreproperties recited in Section VII.B.4 are also expressly contemplated.

VII.C. Vessels Generally

VII.C. A coated vessel or container as described herein and/or preparedaccording to a method described herein can be used for reception and/orstorage and/or delivery of a compound or composition. The compound orcomposition can be sensitive, for example air-sensitive,oxygen-sensitive, sensitive to humidity and/or sensitive to mechanicalinfluences. It can be a biologically active compound or composition, forexample a medicament like insulin or a composition comprising insulin.In another aspect, it can be a biological fluid, optionally a bodilyfluid, for example blood or a blood fraction. In certain aspects of thepresent invention, the compound or composition is a product to beadministrated to a subject in need thereof, for example a product to beinjected, like blood (as in transfusion of blood from a donor to arecipient or reintroduction of blood from a patient back to the patient)or insulin.

VII.C. A coated vessel or container as described herein and/or preparedaccording to a method described herein can further be used forprotecting a compound or composition contained in its interior spaceagainst mechanical and/or chemical effects of the contact surface of theuncoated vessel material. For example, it can be used for preventing orreducing precipitation and/or clotting or platelet activation of thecompound or a component of the composition, for example insulinprecipitation or blood clotting or platelet activation.

VII.C. It can further be used for protecting a compound or compositioncontained in its interior against the environment outside of the vessel,for example by preventing or reducing the entry of one or more compoundsfrom the environment surrounding the vessel into the interior space ofthe vessel. Such environmental compound can be a gas or liquid, forexample an atmospheric gas or liquid containing oxygen, air, and/orwater vapor.

VII.C. A coated vessel as described herein can also be evacuated andstored in an evacuated state. For example, the coating allows bettermaintenance of the vacuum in comparison to a corresponding uncoatedvessel. In one aspect of this embodiment, the coated vessel is a bloodcollection tube. The tube can also contain an agent for preventing bloodclotting or platelet activation, for example EDTA or heparin.

VII.C. Any of the above-described embodiments can be made, for example,by providing as the vessel a length of tubing from about 1 cm to about200 cm, optionally from about 1 cm to about 150 cm, optionally fromabout 1 cm to about 120 cm, optionally from about 1 cm to about 100 cm,optionally from about 1 cm to about 80 cm, optionally from about 1 cm toabout 60 cm, optionally from about 1 cm to about 40 cm, optionally fromabout 1 cm to about 30 cm long, and processing it with a probe electrodeas described below. Particularly for the longer lengths in the aboveranges, it is contemplated that relative motion between the probe andthe vessel can be useful during coating formation. This can be done, forexample, by moving the vessel with respect to the probe or moving theprobe with respect to the vessel.

VII.C. In these embodiments, it is contemplated that the coating can bethinner or less complete than can be preferred for a barrier coating, asthe vessel in some embodiments will not require the high barrierintegrity of an evacuated blood collection tube.

VII.C. As an optional feature of any of the foregoing embodiments thevessel has a central axis.

VII.C. As an optional feature of any of the foregoing embodiments thevessel wall is sufficiently flexible to be flexed at least once at 20°C., without breaking the wall, over a range from at least substantiallystraight to a bending radius at the central axis of not more than 100times as great as the outer diameter of the vessel.

VII.C. As an optional feature of any of the foregoing embodiments thebending radius at the central axis is not more than 90 times as greatas, or not more than 80 times as great as, or not more than 70 times asgreat as, or not more than 60 times as great as, or not more than 50times as great as, or not more than 40 times as great as, or not morethan 30 times as great as, or not more than 20 times as great as, or notmore than 10 times as great as, or not more than 9 times as great as, ornot more than 8 times as great as, or not more than 7 times as great as,or not more than 6 times as great as, or not more than 5 times as greatas, or not more than 4 times as great as, or not more than 3 times asgreat as, or not more than 2 times as great as, or not more than, theouter diameter of the vessel.

VII.C. As an optional feature of any of the foregoing embodiments thevessel wall can be a fluid-contacting contact surface made of flexiblematerial.

VII.C. As an optional feature of any of the foregoing embodiments thevessel lumen can be the fluid flow passage of a pump.

VII.C. As an optional feature of any of the foregoing embodiments thevessel can be a blood bag adapted to maintain blood in good conditionfor medical use.

VII.C., VII.D. As an optional feature of any of the foregoingembodiments the polymeric material can be a silicone elastomer or athermoplastic polyurethane, as two examples, or any material suitablefor contact with blood, or with insulin.

VII.C., VII.D. In an optional embodiment, the vessel has an innerdiameter of at least 2 mm, or at least 4 mm.

VII.C. As an optional feature of any of the foregoing embodiments thevessel is a tube.

VII.C. As an optional feature of any of the foregoing embodiments thelumen has at least two open ends.

VII.C.1. Vessel Containing Viable Blood, Having a Coating Deposited froman Organosilicon Precursor

VII.C.1. Even another embodiment is a blood containing vessel. Severalnon-limiting examples of such a vessel are a blood transfusion bag, ablood sample collection vessel in which a sample has been collected, thetubing of a heart-lung machine, a flexible-walled blood collection bag,or tubing used to collect a patient's blood during surgery andreintroduce the blood into the patient's vasculature. If the vesselincludes a pump for pumping blood, a particularly suitable pump is acentrifugal pump or a peristaltic pump. The vessel has a wall; the wallhas an inner contact surface defining a lumen. The inner contact surfaceof the wall has an at least partial coating of a hydrophobic layer,characterized as defined in the Definition Section. The coating can beas thin as monomolecular thickness or as thick as about 1000 nm. Thevessel contains blood viable for return to the vascular system of apatient disposed within the lumen in contact with the hydrophobic layer.

VII.C.1. An embodiment is a blood containing vessel including a wall andhaving an inner contact surface defining a lumen. The inner contactsurface has an at least partial coating of a hydrophobic layer. Thecoating can also comprise or consist essentially of SiO_(x), where x isas defined in this specification. The thickness of the coating is withinthe range from monomolecular thickness to about 1000 nm thick on theinner contact surface. The vessel contains blood viable for return tothe vascular system of a patient disposed within the lumen in contactwith the hydrophobic layer.

VII.C.2. Coating Deposited from an Organosilicon Precursor ReducesClotting or Platelet Activation of Blood in the Vessel

VII.C.2. Another embodiment is a vessel having a wall. The wall has aninner contact surface defining a lumen and has an at least partialcoating of a hydrophobic layer, where optionally w, x, y, and z are aspreviously defined in the Definition Section. The thickness of thecoating is from monomolecular thickness to about 1000 nm thick on theinner contact surface. The coating is effective to reduce the clottingor platelet activation of blood exposed to the inner contact surface,compared to the same type of wall uncoated with a hydrophobic layer.

VII.C.2. It is contemplated that the incorporation of a hydrophobiclayer will reduce the adhesion or clot forming tendency of the blood, ascompared to its properties in contact with an unmodified polymeric orSiO_(x) contact surface. This property is contemplated to reduce orpotentially eliminate the need for treating the blood with heparin, asby reducing the necessary blood concentration of heparin in a patientundergoing surgery of a type requiring blood to be removed from thepatient and then returned to the patient, as when using a heart-lungmachine during cardiac surgery. It is contemplated that this will reducethe complications of surgery involving the passage of blood through sucha vessel, by reducing the bleeding complications resulting from the useof heparin.

VII.C.2. Another embodiment is a vessel including a wall and having aninner contact surface defining a lumen. The inner contact surface has anat least partial coating of a hydrophobic layer, the thickness of thecoating being from monomolecular thickness to about 1000 nm thick on theinner contact surface, the coating being effective to reduce theclotting or platelet activation of blood exposed to the inner contactsurface.

VII.C.3. Vessel Containing Viable Blood, Having a Coating of Group IIIor IV Element

VII.C.3. Another embodiment is a blood containing vessel having a wallhaving an inner contact surface defining a lumen. The inner contactsurface has an at least partial coating of a composition comprising oneor more elements of Group III, one or more elements of Group IV, or acombination of two or more of these. The thickness of the coating isbetween monomolecular thickness and about 1000 nm thick, inclusive, onthe inner contact surface. The vessel contains blood viable for returnto the vascular system of a patient disposed within the lumen in contactwith the hydrophobic layer.

VII.C.4. Coating of Group III or IV Element Reduces Clotting or PlateletActivation of Blood in the Vessel

VII.C.4. Optionally, in the vessel of the preceding paragraph, thecoating of the Group III or IV Element is effective to reduce theclotting or platelet activation of blood exposed to the inner contactsurface of the vessel wall.

VII.D. Pharmaceutical Delivery Vessels

VII.D. A coated vessel or container as described herein can be used forpreventing or reducing the escape of a compound or composition containedin the vessel into the environment surrounding the vessel.

Further uses of the coating and vessel as described herein, which areapparent from any part of the description and claims, are alsocontemplated.

VII.D.1. Vessel Containing Insulin, Having a Coating Deposited from anOrganosilicon Precursor

VII.D.1. Another embodiment is an insulin containing vessel including awall having an inner contact surface defining a lumen. The inner contactsurface has an at least partial coating of a hydrophobic layer,characterized as defined in the Definition Section. The coating can befrom monomolecular thickness to about 1000 nm thick on the inner contactsurface. Insulin is disposed within the lumen in contact with theSi_(w)O_(x)C_(y)H_(z) coating.

VII.D.1. Still another embodiment is an insulin containing vesselincluding a wall and having an inner contact surface defining a lumen.The inner contact surface has an at least partial coating of ahydrophobic layer, characterized as defined in the Definition Section,the thickness of the coating being from monomolecular thickness to about1000 nm thick on the inner contact surface. Insulin, for examplepharmaceutical insulin FDA approved for human use, is disposed withinthe lumen in contact with the hydrophobic layer.

VII.D.1. It is contemplated that the incorporation of a hydrophobiclayer, characterized as defined in the Definition Section, will reducethe adhesion or precipitation forming tendency of the insulin in adelivery tube of an insulin pump, as compared to its properties incontact with an unmodified polymeric contact surface. This property iscontemplated to reduce or potentially eliminate the need for filteringthe insulin passing through the delivery tube to remove a solidprecipitate.

VII.D.2. Coating Deposited from an Organosilicon Precursor ReducesPrecipitation of Insulin in the Vessel

VII.D.2. Optionally, in the vessel of the preceding paragraph, thecoating of a hydrophobic layer is effective to reduce the formation of aprecipitate from insulin contacting the inner contact surface, comparedto the same contact surface absent the hydrophobic layer.

VII.D.2. Even another embodiment is a vessel again comprising a wall andhaving an inner contact surface defining a lumen. The inner contactsurface includes an at least partial coating of a hydrophobic layer. Thethickness of the coating is in the range from monomolecular thickness toabout 1000 nm thick on the inner contact surface. The coating iseffective to reduce the formation of a precipitate from insulincontacting the inner contact surface.

VII.D.3. Vessel Containing Insulin, Having a Coating of Group III or IVElement

VII.D.3. Another embodiment is an insulin containing vessel including awall having an inner contact surface defining a lumen. The inner contactsurface has an at least partial coating of a composition comprisingcarbon, one or more elements of Group III, one or more elements of GroupIV, or a combination of two or more of these. The coating can be frommonomolecular thickness to about 1000 nm thick on the inner contactsurface. Insulin is disposed within the lumen in contact with thecoating.

VII.D.4. Coating of Group III or IV Element Reduces Precipitation ofInsulin in the Vessel

VII.D.4. Optionally, in the vessel of the preceding paragraph, thecoating of a composition comprising carbon, one or more elements ofGroup III, one or more elements of Group IV, or a combination of two ormore of these, is effective to reduce the formation of a precipitatefrom insulin contacting the inner contact surface, compared to the samecontact surface absent the coating.

Other Types of Medical Devices

A wide variety of medical devices having one or more coatings as definedin the present disclosure are contemplated. Some specific examples ofsuch devices follow.

Anesthesia ventilators are contemplated employing an SiO_(x) barriercoating on a bellows cylinder. The ventilator cylinders can be SiO_(x)coated to eliminate gas diffusion.

Buccal sample cassettes are contemplated employing an SiO_(x) barrier.

Capillary Blood Collection devices are contemplated employing an SiO_(x)barrier to keep constituents of the device wall from leaching into theblood or vice versa.

Centrifuge components, in particular centrifuge vials, tubes, or othercontainers are contemplated employing an SiO_(x) barrier to providereduced plastic contamination.

Containers are contemplated employing an SiO_(x) barrier where plasticcontamination control or O₂ barrier control is desirable.

Drug-Eluting Stents, for example Self-Expandable Metallic Stents,Vascular Ring Connectors, and Vascular Stents are contemplated employingan SiO_(x)C_(y) or SiN_(x)C_(y) controlled porosity layer to control therate of drug elution from the stent.

Inhalers are contemplated employing an SiO_(x) barrier. A coated plastictube in the device inhibits vapor absorption.

Insulin pens are contemplated employing an SiO_(x) barrier coatedcartridge, analogous to the coating contemplated for the barrel of asyringe.

Insulin pumps are contemplated employing an SiO_(x) barrier to improvedelivery and provide a barrier in the reservoir of the pump.

IV Adapters are contemplated employing an SiO_(x) barrier to preventplastic extraction into blood.

Medical ventilators are contemplated employing an SiO_(x) antifog layerto prevent the facemask from fogging in use.

Pipettes are contemplated employing an SiO_(x) barrier coating.

Sample collection containers are contemplated employing an SiO_(x)wetting/barrier coating.

Sample Collection Tubes and Storage Devices are contemplated employingan SiO_(x) wetting/barrier coating.

Shaker flasks are contemplated employing an SiO_(x) barrier coating forreduced leaching to or from their glass or plastic walls.

Tissue grinders are contemplated employing an SiO_(x) abrasion/barriercoating, at least in the grinder container.

Urine sample cassettes are contemplated employing an SiO_(x) barriercoating in the sample container, as explained above for samplecontainers generally.

Ankle replacements are contemplated employing an SiO_(x) coating on themetal/ceramic prosthesis.

Implanted cardiac devices such as Artificial Pacemakers andDefibrillators and associated parts are contemplated employing anSiO_(x) barrier coating.

An artificial pancreas is contemplated employing an SiO_(x) barriercoating.

Atherectomy catheters are contemplated employing an SiO_(x)hard/wettable coating. Atherectomy is a procedure that utilizes acatheter with a sharp blade on the end to remove plaque from a bloodvessel.

Cell Lifters, Cell Scrapers, and Cell Spreaders, which are polyethylenemolded devices for recombinant cell removal, are contemplated employingan SiO_(x) barrier coating to prevent plastic/additives contamination.

Cornea implants are contemplated employing an SiO_(x) barrier coating toprevent plastic extractables in the eye.

Cover glasses are contemplated employing an SiO_(x) barrier coating toprovide reduced Na, K, and B leaching into a sample.

Plastic depression microscopic slides are contemplated employing anSiO_(x) barrier coating for reduced interaction with plastic additives.

Direct Testing and Serology devices are contemplated employing anSiO_(x) barrier coating for plastic extractables control.

Flat plastic microscopic slides are contemplated employing an SiO_(x)barrier coating for control of plastic contact (wettability).

Glaucoma valves made of plastic are contemplated employing an SiO_(x)hydrophilic coating for improved wettability of plastic.

Hip Prostheses and re-constructive prosthesis replacements, other jointand cartilage replacements, and orthopedic implants, such as for thehand, knee, and shoulder are contemplated, optionally employing a thick(more than one micron, alternatively several microns) SiO_(x) anti-wearcoating on the metal/plastic sleeve or other wear parts.

Medicine and contraceptive implants and implantable devices, for examplesub-dermal implants are contemplated employing an SiO_(x)C_(y) orSiN_(x)C_(y) controlled porosity layer to provide controlled release ofthe medicine.

Lancets, scalpels, razor blades, and sewing and hypodermic needles arecontemplated employing an SiO_(x)C_(y) or SiN_(x)C_(y) lubricity layerto facilitate piercing skin and other tissues and objects and reducefriction.

Medical grafting material such as excised skin is contemplated employingan SiO_(x) barrier coating to retain moisture. It is contemplated as onealternative that the barrier coating would dissolve when the graftingmaterial was applied, due to contact with body fluids or pretreatment,so it would not impede fluid exchange.

Microtiter plates made of plastic are contemplated employing an SiO_(x)barrier coating.

Molecular Diagnostics devices such as “lab on chip” devices,microsensors and nanosensors are contemplated employing an SiO_(x) gasbarrier coating and/or an SiO_(x)C_(y) or SiN_(x)C_(y) hydrophobic layeras a water barrier.

Mycobacteria Testing Devices such as growth indicator tubes arecontemplated employing an SiO_(x) wettability coating, for improvedperformance.

Catheters, for example Angioplasty Catheters, Urethral Catheters, andPeripherally Inserted Central Catheters (PICCs) are contemplatedemploying an SiO_(x)C_(y) or SiN_(x)C_(y) lubricity layer to easeinsertion and removal and reduce friction.

Shunt (medical) skin implants are contemplated employing an SiO_(x)wettability coating.

Stent grafts and Stents are contemplated employing an SiO_(x)wettability coating to provide improved in vivo grafting.

Transdermal implants are contemplated employing an SiO_(x)C_(y) orSiN_(x)C_(y) controlled porosity layer.

Ultrasonic nebulizers are contemplated employing an SiO_(x)C_(y) orSiN_(x)C_(y) controlled porosity or hydrophobic layer to control dropsize.

Unicompartmental knee arthroplasty devices are contemplated employing athick SiO_(x) anti-wear coating.

Microchip implants (for humans or animals) are contemplated employing adiamond-like carbon (DLC)-based water and water vapor barrier.

Needleless and conventional IV Connectors are contemplated employing anSiO_(x)C_(y) or SiN_(x)C_(y) lubricity layer to reduce the necessaryconnection and disconnection force. The SiO_(x)C_(y) or SiN_(x)C_(y)layer can optionally be supplemented with a silver antimicrobial layerand/or an SiO_(x) barrier coating to prevent plastic extract into blood.

Auditory brainstem implants are contemplated employing a diamond-likecarbon (DLC) based water and water vapor barrier, particularly for theimplanted sensor or power unit.

Goggles are contemplated employing an SiO_(x)C_(y) or SiN_(x)C_(y)hydrophobic layer to provide antifogging lenses.

Stains and Reagents in encapsulated or particulate form are contemplatedemploying an SiO_(x)C_(y) or SiN_(x)C_(y) controlled porosity layer toprovide controlled encapsulation/release.

Prostatic stents are contemplated employing an SiO_(x)C_(y) orSiN_(x)C_(y) controlled porosity layer to provide controlled release ofmaterial.

Sutures and surgical staples are contemplated employing an SiO_(x)C_(y)or SiN_(x)C_(y) lubricity layer to make them slide more easily wheninserted and removed.

Dehydrated Culture Media devices are contemplated employing an SiO_(x)barrier coating so their plastic constituents do not extract intoculture media.

Cochlear implants are contemplated employing an SiO_(x) barrier coatingto prevent the ingress of ear wax and body fluids.

Petri dishes are contemplated employing an SiO_(x) barrier coating.

Sacral nerve stimulator wires and implants are contemplated employing anSiO_(x) barrier coating.

Peritoneovenous shunts and fluid drains and Portacaval shunts made ofplastic are contemplated employing an SiO_(x) wettability coating.

Surgical microscopes are contemplated employing an SiO_(x)wetting/barrier coating to prevent fogging of the visual aperture.

Plastic Right-to-Left Shunts are contemplated employing an SiO_(x)wettability coating.

Static Control Supplies are contemplated employing an SiO_(x)wettability coating, as adsorbed moisture on the coating will reducestatic.

WORKING EXAMPLES Basic Protocols for Forming and Coating Tubes andSyringe Barrels

The vessels tested in the subsequent working examples were formed andcoated according to the exemplary protocols set out in U.S. Pat. No.7,985,188 as incorporated by reference, except as otherwise indicated inindividual examples. Whenever parameter values were changed incomparison to these typical values, this will be indicated in thesubsequent working examples. The same applies to the type andcomposition of the process gas.

Example 1

V. In the following test, hexamethyldisiloxane (HMDSO) was used as theorganosilicon (“O—Si”) feed to PECVD apparatus of FIG. 1 to apply anSiO_(x) coating on the internal contact surface of a cyclic olefincopolymer (COC) tube as described in the Protocol for Forming COC Tube.The deposition conditions are summarized in the Protocol for CoatingTube Interior with SiO_(x) and Table 1. The control was the same type oftube to which no barrier coating was applied. The coated and uncoatedtubes were then tested for their oxygen transmission rate (OTR) andtheir water vapor transmission rate (WVTR).

V. Referring to Table 1, the uncoated COC tube had an OTR of 0.215cc/tube/day. Tubes A and B subjected to PECVD for 14 seconds had anaverage OTR of 0.0235 cc/tube/day. These results show that the SiO_(x)coating provided an oxygen transmission BIF over the uncoated tube of9.1. In other words, the SiO_(x) barrier coating reduced the oxygentransmission through the tube to less than one ninth its value withoutthe coating.

V. Tube C subjected to PECVD for 7 seconds had an OTR of 0.026. Thisresult shows that the SiO_(x) coating provided an OTR BIF over theuncoated tube of 8.3. In other words, the SiO_(x) barrier coatingapplied in 7 seconds reduced the oxygen transmission through the tube toless than one eighth of its value without the coating.

V. The relative WVTRs of the same barrier coatings on COC tubes werealso measured. The uncoated COC tube had a WVTR of 0.27 mg/tube/day.Tubes A and B subjected to PECVD for 14 seconds had an average WVTR of0.10 mg/tube/day or less. Tube C subjected to PECVD for 7 seconds had aWVTR of 0.10 mg/tube/day. This result shows that the SiO_(x) coatingprovided a water vapor transmission barrier improvement factor (WVTRBIF) over the uncoated tube of about 2.7. This was a surprising result,since the uncoated COC tube already has a very low WVTR.

Example 2

V. A series of PET tubes, made according to the Protocol for Forming PETTube, were coated with SiO_(x) according to the Protocol for CoatingTube Interior with SiO_(x) under the conditions reported in Table 2.Controls were made according to the Protocol for Forming PET Tube, butleft uncoated. OTR and WVTR samples of the tubes were prepared byepoxy-sealing the open end of each tube to an aluminum adaptor.

V. In a separate test, using the same type of coated PET tubes,mechanical scratches of various lengths were induced with a steel needlethrough the interior coating, and the OTR BIF was tested. Controls wereeither left uncoated or were the same type of coated tube without aninduced scratch. The OTR BIF, while diminished, was still improved overuncoated tubes (Table 2A).

V. Tubes were tested for OTR as follows. Each sample/adaptor assemblywas fitted onto a MOCON® Oxtran 2/21 Oxygen Permeability Instrument.Samples were allowed to equilibrate to transmission rate steady state(1-3 days) under the following test conditions:

-   -   Test Gas: Oxygen    -   Test Gas Concentration: 100%    -   Test Gas Humidity: 0% relative humidity    -   Test Gas Pressure: 760 mmHg    -   Test Temperature: 23.0° C. (73.4° F.)    -   Carrier Gas: 98% nitrogen, 2% hydrogen    -   Carrier Gas Humidity: 0% relative humidity

V. The OTR is reported as average of two determinations in Table 2.

V. Tubes were tested for WVTR as follows. The sample/adaptor assemblywas fitted onto a MOCON® Permatran-W 3/31 Water Vapor PermeabilityInstrument. Samples were allowed to equilibrate to transmission ratesteady state (1-3 days) under the following test conditions:

-   -   Test Gas: Water Vapor    -   Test Gas Concentration: NA    -   Test Gas Humidity: 100% relative humidity    -   Test Gas Temperature: 37.8(° C.) 100.0(° F.)    -   Carrier Gas: Dry nitrogen    -   Carrier Gas Humidity: 0% relative humidity

V. The WVTR is reported as average of two determinations in Table 2.

Example 3

A series of syringe barrels were made according to the Protocol forForming COC Syringe barrel. The syringe barrels were either barriercoated with SiO_(x) or not under the conditions reported in the Protocolfor Coating COC Syringe barrel Interior with SiO_(x) modified asindicated in Table 3.

OTR and WVTR samples of the syringe barrels were prepared byepoxy-sealing the open end of each syringe barrel to an aluminumadaptor. Additionally, the syringe barrel capillary ends were sealedwith epoxy. The syringe-adapter assemblies were tested for OTR or WVTRin the same manner as the PET tube samples, again using a MOCON® Oxtran2/21 Oxygen Permeability Instrument and a MOCON® Permatran-W 3/31 WaterVapor Permeability Instrument. The results are reported in Table 3.

Example 4 Composition Measurement of Plasma Coatings Using X-RayPhotoelectron Spectroscopy (XPS)/Electron Spectroscopy for ChemicalAnalysis (ESCA) Contact Surface Analysis

V.A. PET tubes made according to the Protocol for Forming PET Tube andcoated according to the Protocol for Coating Tube Interior with SiO_(x)were cut in half to expose the inner tube contact surface, which wasthen analyzed using X-ray photoelectron spectroscopy (XPS).

V.A. The XPS data was quantified using relative sensitivity factors anda model which assumes a homogeneous layer. The analysis volume is theproduct of the analysis area (spot size or aperture size) and the depthof information. Photoelectrons are generated within the X-raypenetration depth (typically many microns), but only the photoelectronswithin the top three photoelectron escape depths are detected. Escapedepths are on the order of 15-35 Å, which leads to an analysis depth of˜50-100 Å. Typically, 95% of the signal originates from within thisdepth.

V.A. Table 5 provides the atomic ratios of the elements detected. Theanalytical parameters used in for XPS are as follows:

Instrument PHI Quantum 2000 X-ray source Monochromated Alk_(α) 1486.6 eVAcceptance Angle ±23° Take-off angle 45° Analysis area 600 μm ChargeCorrection C1s 284.8 eV Ion Gun Conditions Ar⁺, 1 keV, 2 × 2 mm rasterSputter Rate 15.6 Å/min (SiO₂ Equivalent)

V.A. XPS does not detect hydrogen or helium. Values given are normalizedto Si=1 for the experimental number (last row) using the elementsdetected, and to O=1 for the uncoated polyethylene terephthalatecalculation and example. Detection limits are approximately 0.05 to 1.0atomic percent. Values given are alternatively normalized to 100% Si+O+Catoms.

V.A. The Inventive Example has an Si/O ratio of 2.4 indicating anSiO_(x) composition, with some residual carbon from incomplete oxidationof the coating. This analysis demonstrates the composition of an SiO_(x)barrier layer applied to a polyethylene terephthalate tube according tothe present invention.

V.A. Table 4 shows the thickness of the SiO_(x) samples, determinedusing TEM according to the following method. Samples were prepared forFocused Ion Beam (FIB) cross-sectioning by coating the samples with asputtered layer of platinum (50-100 nm thick) using a K575X Emitechcoating system. The coated samples were placed in an FEI FIB200 FIBsystem. An additional layer of platinum was FIB-deposited by injectionof an organometallic gas while rastering the 30 kV gallium ion beam overthe area of interest. The area of interest for each sample was chosen tobe a location half way down the length of the tube. Thin cross sectionsmeasuring approximately 15 μm (“micrometers”) long, 2 μm wide and 15 μmdeep were extracted from the die contact surface using a proprietaryin-situ FIB lift-out technique. The cross sections were attached to a200 mesh copper TEM grid using FIB-deposited platinum. One or twowindows in each section, measuring about 8 μm wide, were thinned toelectron transparency using the gallium ion beam of the FEI FIB.

V.C. Cross-sectional image analysis of the prepared samples wasperformed utilizing a Transmission Electron Microscope (TEM). Theimaging data was recorded digitally.

The sample grids were transferred to a Hitachi HF2000 transmissionelectron microscope. Transmitted electron images were acquired atappropriate magnifications. The relevant instrument settings used duringimage acquisition are given below.

Instrument Transmission Electron Microscope Manufacturer/Model HitachiHF2000 Accelerating Voltage 200 kV Condenser Lens 1 0.78 Condenser Lens2 0 Objective Lens 6.34 Condenser Lens Aperture #1 Objective LensAperture for #3 imaging Selective Area Aperture for N/A SAD

Example 5 Plasma Uniformity

V.A. COC syringe barrels made according to the Protocol for Forming COCSyringe barrel were treated using the Protocol for Coating COC SyringeBarrel Interior with SiO_(x), with the following variations. Threedifferent modes of plasma generation were tested for coating syringebarrels such as 250 with SiO_(x) films. V.A. In Mode 1, hollow cathodeplasma ignition was generated in the gas inlet 310, restricted area 292and processing vessel lumen 304, and ordinary or non-hollow-cathodeplasma was generated in the remainder of the vessel lumen 300.

V.A. In Mode 2, hollow cathode plasma ignition was generated in therestricted area 292 and processing vessel lumen 304, and ordinary ornon-hollow-cathode plasma was generated in the remainder of the vessellumen 300 and gas inlet 310.

V.A. In Mode 3, ordinary or non-hollow-cathode plasma was generated inthe entire vessel lumen 300 and gas inlet 310. This was accomplished byramping up power to quench any hollow cathode ignition. Table 6 showsthe conditions used to achieve these modes.

V.A. The syringe barrels 250 were then exposed to a ruthenium oxidestaining technique. The stain was made from sodium hypochlorite bleachand Ru^((III)) chloride hydrate. 0.2 g of Ru^((III)) chloride hydratewas put into a vial. 10 ml bleach were added and mixed thoroughly untilthe Ru(III) chloride hydrate dissolved.

V.A. Each syringe barrel was sealed with a plastic Luer seal and 3 dropsof the staining mixture were added to each syringe barrel. The syringebarrels were then sealed with aluminum tape and allowed to sit for 30-40minutes. In each set of syringe barrels tested, at least one uncoatedsyringe barrel was stained. The syringe barrels were stored with therestricted area 292 facing up.

V.A. Based on the staining, the following conclusions were drawn:

V.A. 1. The stain started to attack the uncoated (or poorly coated)areas within 0.25 hours of exposure.

V.A. 2. Ignition in the restricted area 292 resulted in SiO_(x) coatingof the restricted area 292.

V.A. 3. The best syringe barrel was produced by the test with no hollowcathode plasma ignition in either the gas inlet 310 or the restrictedarea 292. Only the restricted opening 294 was stained, most likely dueto leaking of the stain.

V.A. 4. Staining is a good qualitative tool to guide uniformity work.

V.A. Based on all of the above, we concluded:

V.A. 1. Under the conditions of the test, hollow cathode plasma ineither the gas inlet 310 or the restricted area 292 led to pooruniformity of the coating.

V.A. 2. The best uniformity was achieved with no hollow cathode plasmain either the gas inlet 310 or the restricted area 292.

Example 6

Interference Patterns from Reflectance Measurements—Prophetic Example

VI.A. Using a UV-Visible Source (Ocean Optics DH2000-BAL DeuteriumTungsten 200-1000 nm), a fiber optic reflection probe (combinationemitter/collector Ocean Optics QR400-7 SR/BX with approximately 3 mmprobe area), miniature detector (Ocean Optics HR4000CG UV-NIRSpectrometer), and software converting the spectrometer signal to atransmittance/wavelength graph on a laptop computer, an uncoated PETtube Becton Dickinson (Franklin Lakes, N.J., USA) Product No. 36670313×75 mm (no additives) is scanned (with the probe emitting andcollecting light radially from the centerline of the tube, thus normalto the coated contact surface) both about the inner circumference of thetube and longitudinally along the inner wall of the tube, with theprobe, with no observable interference pattern observed. Then a BectonDickinson Product No. 366703 13×75 mm (no additives) SiO_(x)plasma-coated BD 366703 tube is coated with a 20 nanometer thick SiO₂coating as described in Protocol for Coating Tube Interior with SiO_(x).This tube is scanned in a similar manner as the uncoated tube. A clearinterference pattern is observed with the coated tube, in which certainwavelengths were reinforced and others canceled in a periodic pattern,indicating the presence of a coating on the PET tube.

Example 7

Enhanced Light Transmission from Integrating Sphere Detection

VI.A. The equipment used was a Xenon light source (Ocean OpticsHL-2000-HP-FHSA-20 W output Halogen Lamp Source (185-2000 nm)), anIntegrating Sphere detector (Ocean Optics ISP-80-8-I) machined to accepta PET tube into its interior, and HR2000+ES Enhanced Sensitivity UV.VISspectrometer, with light transmission source and light receiver fiberoptic sources (QP600-2-UV-VIS-600 um Premium Optical FIBER, UV/VIS, 2m), and signal conversion software (SPECTRASUITE—Cross-platformSpectroscopy Operating SOFTWARE). An uncoated PET tube made according tothe Protocol for Forming PET Tube was inserted onto a TEFZEL Tube Holder(Puck), and inserted into the integrating sphere. With the Spectrasuitesoftware in absorbance mode, the absorption (at 615 nm) was set to zero.An SiO_(x) coated tube made according to the Protocol for Forming PETTube and coated according to the Protocol for Coating Tube Interior withSiO_(x) (except as varied in Table 16) was then mounted on the puck,inserted into the integrating sphere and the absorbance recorded at 615nm wavelength. The data is recorded in Table 16.

VI.A. With the SiO_(x) coated tubes, an increase in absorption relativeto the uncoated article was observed; increased coating times resultedin increased absorption. The measurement took less than one second.

VI.A. These spectroscopic methods should not be considered limited bythe mode of collection (for example, reflectance vs. transmittance vs.absorbance), the frequency or type of radiation applied, or otherparameters.

Example 8 Wetting Tension—Plasma Coated PET Tube Examples

VII.A.1.a.ii. The wetting tension method is a modification of the methoddescribed in ASTM D 2578. Wetting tension is a specific measure for thehydrophobicity or hydrophilicity of a contact surface. This method usesstandard wetting tension solutions (called dyne solutions) to determinethe solution that comes nearest to wetting a plastic film contactsurface for exactly two seconds. This is the film's wetting tension.

VII.A.1.a.ii. The procedure utilized is varied from ASTM D 2578 in thatthe substrates are not flat plastic films, but are tubes made accordingto the Protocol for Forming PET Tube and (except for controls) coatedaccording to the Protocol for Coating Tube Interior with Hydrophobiclayer. A silicone coated glass syringe (Becton Dickinson Hypak® PRTCglass prefillable syringe with Luer-lok® tip) (1 mL) was also tested.The results of this test are listed in Table 10.

VII.A.1.a.ii. Surprisingly, plasma coating of uncoated PET tubes (40dynes/cm) can achieve either higher (more hydrophilic) or lower (morehydrophobic) energy contact surfaces using the same hexamethyldisiloxane(HMDSO) feed gas, by varying the plasma process conditions. A thin(approximately 20-40 nanometers) SiO_(x) coating made according to theProtocol for Coating Tube Interior with SiO_(x) (data not shown in thetables) provides similar wettability as hydrophilic bulk glasssubstrates. A thin (less than about 100 nanometers) hydrophobic layermade according to the Protocol for Coating Tube Interior withHydrophobic layer provides similar non-wettability as hydrophobicsilicone fluids (data not shown in the tables).

Example 9 Vacuum Retention Study of Tubes Via Accelerated Ageing

VII.A.3 Accelerated ageing offers faster assessment of long termshelf-life products. Accelerated ageing of blood tubes for vacuumretention is described in U.S. Pat. No. 5,792,940, Column 1, Lines11-49.

VII.A.3 Three types of polyethylene terephthalate (PET) 13×75 mm (0.85mm thick walls) molded tubes were tested:

-   -   Becton Dickinson Product No. 366703 13×75 mm (no additives) tube        (shelf life 545 days or 18 months), closed with Hemogard® system        red stopper and uncolored guard [commercial control];    -   PET tubes made according to the Protocol for Forming PET Tube,        closed with the same type of Hemogard® system red stopper and        uncolored guard [internal control]; and    -   injection molded PET 13×75 mm tubes, made according to the        Protocol for Forming PET Tube, coated according to the Protocol        for Coating Tube Interior with SiO_(x) closed with the same type        of Hemogard® system red stopper and uncolored guard [inventive        sample].

VII.A.3 The BD commercial control was used as received. The internalcontrol and inventive samples were evacuated and capped with the stoppersystem to provide the desired partial pressure (vacuum) inside the tubeafter sealing. All samples were placed into a three gallon (3.8 L) 304SS wide mouth pressure vessel (Sterlitech No. 740340). The pressurevessel was pressurized to 48 psi (3.3 atm, 2482 mm·Hg). Water volumedraw change determinations were made by (a) removing 3-5 samples atincreasing time intervals, (b) permitting water to draw into theevacuated tubes through a 20 gauge blood collection adaptor from a oneliter plastic bottle reservoir, (c) and measuring the mass change beforeand after water draw.

VII.A.3 Results are indicated on Table 11.

VII.A.3 The Normalized Average Decay Rate is calculated by dividing thetime change in mass by the number of pressurization days and initialmass draw [mass change/(days x initial mass)]. The Accelerated Time to10% Loss (months) is also calculated. Both data are listed in Table 12.

VII.A.3 This data indicates that both the commercial control anduncoated internal control have identical vacuum loss rates, andsurprisingly, incorporation of a SiO_(x) coating on the PET interiorwalls improves vacuum retention time by a factor of 2.1.

Example 10 Lubricity Layers

VII.B.1.a. The following materials were used in this test:

-   -   Commercial (BD Hypak® PRTC) glass prefillable syringes with        Luer-lok® tip) (ca 1 mL)    -   COC syringe barrels made according to the Protocol for Forming        COC Syringe barrel;    -   Commercial plastic syringe plungers with elastomeric tips taken        from Becton Dickinson Product No. 306507 (obtained as saline        prefilled syringes);    -   Normal saline solution (taken from the Becton-Dickinson Product        No. 306507 prefilled syringes);    -   Dillon Test Stand with an Advanced Force Gauge (Model AFG-50N)    -   Syringe holder and drain jig (fabricated to fit the Dillon Test        Stand)

VII.B.1.a. The following procedure was used in this test.

VII.B.1.a. The jig was installed on the Dillon Test Stand. The platformprobe movement was adjusted to 6 in/min (2.5 mm/sec) and upper and lowerstop locations were set. The stop locations were verified using an emptysyringe and barrel. The commercial saline-filled syringes were labeled,the plungers were removed, and the saline solution was drained via theopen ends of the syringe barrels for re-use. Extra plungers wereobtained in the same manner for use with the COC and glass barrels.

VII.B.1.a. Syringe plungers were inserted into the COC syringe barrelsso that the second horizontal molding point of each plunger was evenwith the syringe barrel lip (about 10 mm from the tip end). Usinganother syringe and needle assembly, the test syringes were filled viathe capillary end with 2-3 milliliters of saline solution, with thecapillary end uppermost. The sides of the syringe were tapped to removeany large air bubbles at the plunger/fluid interface and along thewalls, and any air bubbles were carefully pushed out of the syringewhile maintaining the plunger in its vertical orientation.

VII.B.1.a. Each filled syringe barrel/plunger assembly was installedinto the syringe jig. The test was initiated by pressing the down switchon the test stand to advance the moving metal hammer toward the plunger.When the moving metal hammer was within 5 mm of contacting the top ofthe plunger, the data button on the Dillon module was repeatedly tappedto record the force at the time of each data button depression, frombefore initial contact with the syringe plunger until the plunger wasstopped by contact with the front wall of the syringe barrel.

VII.B.1.a. All benchmark and coated syringe barrels were run with fivereplicates (using a new plunger and barrel for each replicate).

VII.B.1.a. COC syringe barrels made according to the Protocol forForming COC Syringe barrel were coated with an OMCTS lubricity layeraccording to the Protocol for Coating COC Syringe Barrel Interior withOMCTS Lubricity layer, assembled and filled with saline, and tested asdescribed above in this Example for lubricity layers. The polypropylenechamber used per the Protocol for Coating COC Syringe Barrel Interiorwith OMCTS Lubricity layer allowed the OMCTS vapor (and oxygen, ifadded—see Table 13) to flow through the syringe barrel and through thesyringe capillary into the polypropylene chamber (although a lubricitylayer is not needed in the capillary section of the syringe in thisinstance). Several different coating conditions were tested, as shown inpreviously mentioned Table 13. All of the depositions were completed onCOC syringe barrels from the same production batch.

The coated samples were then tested using the plunger sliding force testper the protocol of this Example, yielding the results in Table 13, inEnglish and metric force units. The data shows clearly that low powerand no oxygen provided the lowest plunger sliding force for COC andcoated COC syringes. Note that when oxygen was added at lower power (6W) (the lower power being a favorable condition) the plunger slidingforce increased from 1.09 lb, 0.49 Kg (at Power=11 W) to 2.27 lb., 1.03Kg. This indicates that the addition of oxygen can be undesirable incertain circumstances to achieve the lowest possible plunger slidingforce.

VII.B.1.a. Note also that the best plunger sliding force (Power=11 W,plunger sliding force=1.09 lb, 0.49 Kg) was very near the currentindustry standard of silicone coated glass (plunger sliding force=0.58lb, 0.26 Kg), while avoiding the problems of a glass syringe such asbreakability and a more expensive manufacturing process. With additionaloptimization, values equal to or better than the current glass withsilicone performance are expected to be achieved.

VII.B.1.a. The samples were created by coating COC syringe barrelsaccording to the Protocol for Coating COC Syringe Barrel Interior withOMCTS Lubricity layer. An alternative embodiment of the technologyherein, would apply the lubricity layer over another thin film coating,such as SiO_(x), for example applied according to the Protocol forCoating COC Syringe barrel Interior with SiO_(x).

Example 11

Improved Syringe Barrel Lubricity layer

VII.B.1.a. The force required to expel a 0.9 percent saline payload froma syringe through a capillary opening using a plastic plunger wasdetermined for inner wall-coated syringes.

VII.B.1.a. Three types of COC syringe barrels made according to theProtocol for Forming COC Syringe barrel were tested: one type having nointernal coating [Uncoated Control], another type with ahexamethyldisiloxane (HMDSO)-based plasma coated internal wall coating[HMDSO Control] according to the Protocol for Coating COC Syringe BarrelInterior with HMDSO Coating, and a third type with anoctamethylcyclotetrasiloxane [OMCTS-Inventive Example]-based plasmacoated internal wall coating applied according to the Protocol forCoating COC Syringe Barrel Interior with OMCTS Lubricity layer. Freshplastic plungers with elastomeric tips taken from BD ProductBecton-Dickinson Product No. 306507 were used for all examples. Salinefrom Product No. 306507 was also used.

VII.B.1.a. The plasma coating method and apparatus for coating thesyringe barrel inner walls is described in other experimental sectionsof this application. The specific coating parameters for the HMDSO-basedand OMCTS-based coatings are listed in the Protocol for Coating COCSyringe Barrel Interior with HMDSO Coating, the Protocol for Coating COCSyringe barrel Interior with OMCTS Lubricity layer, and Table 14.

VII.B.1.a. The plunger is inserted into the syringe barrel to about 10millimeters, followed by vertical filling of the experimental syringethrough the open syringe capillary with a separate saline-filledsyringe/needle system. When the experimental syringe has been filledinto the capillary opening, the syringe is tapped to permit any airbubbles adhering to the inner walls to release and rise through thecapillary opening.

VII.B.1.a. The filled experimental syringe barrel/plunger assembly isplaced vertically into a home-made hollow metal jig, the syringeassembly being supported on the jig at the finger flanges. The jig has adrain tube at the base and is mounted on Dillon Test Stand with AdvancedForce Gauge (Model AFG-50N). The test stand has a metal hammer, movingvertically downward at a rate of six inches (152 millimeters) perminute. The metal hammer contacts the extended plunger expelling thesaline solution through the capillary. Once the plunger has contactedthe syringe barrel/capillary interface the experiment is stopped.

VII.B.1.a. During downward movement of the metal hammer/extendedplunger, resistance force imparted on the hammer as measured on theForce Gauge is recorded on an electronic spreadsheet. From thespreadsheet data, the maximum force for each experiment is identified.

VII.B.1.a. Table 14 lists for each Example the Maximum Force averagefrom replicate coated COC syringe barrels and the Normalized MaximumForce as determined by division of the coated syringe barrel MaximumForce average by the uncoated Maximum Force average.

VII.B.1.a. The data indicates all OMCTS-based inner wall plasma coatedCOC syringe barrels (Inventive Examples C, E, F, G, H) demonstrate muchlower plunger sliding force than uncoated COC syringe barrels (uncoatedControl Examples A & D) and surprisingly, also much lower plungersliding force than HMDSO-based inner wall plasma coated COC syringebarrels (HMDSO control Example B). More surprising, an OMCTS-basedcoating over a silicon oxide (SiO_(x)) gas barrier coating maintainsexcellent low plunger sliding force (Inventive Example F). The bestplunger sliding force was Example C (Power=8, plunger sliding force=1.1lb, 0.5 Kg). It was very near the current industry standard of siliconecoated glass (plunger sliding force=0.58 lb., 0.26 Kg.), while avoidingthe problems of a glass syringe such as breakability and a moreexpensive manufacturing process. With additional optimization, valuesequal to or better than the current glass with silicone performance areexpected to be achieved.

Example 12

Fabrication of COC Syringe Barrel with Exterior Coating—PropheticExample

VII.B.1.c. A COC syringe barrel formed according to the Protocol forForming COC Syringe barrel is sealed at both ends with disposableclosures. The capped COC syringe barrel is passed through a bath ofDaran® 8100 Saran Latex (Owensboro Specialty Plastics). This latexcontains five percent isopropyl alcohol to reduce the contact surfacetension of the composition to 32 dynes/cm). The latex compositioncompletely wets the exterior of the COC syringe barrel. After drainingfor 30 seconds, the coated COC syringe barrel is exposed to a heatingschedule comprising 275° F. (135° C.) for 25 seconds (latex coalescence)and 122° F. (50° C.) for four hours (finish cure) in respective forcedair ovens. The resulting PVdC film is 1/10 mil (2.5 microns) thick. TheCOC syringe barrel and PVdC-COC laminate COC syringe barrel are measuredfor OTR and WVTR using a MOCON brand Oxtran 2/21 Oxygen PermeabilityInstrument and Permatran-W 3/31 Water Vapor Permeability Instrument,respectively.

VII.B.1.c. Predicted OTR and WVTR values are listed in Table 15, whichshows the expected Barrier Improvement Factor (BIF) for the laminatewould be 4.3 (OTR-BIF) and 3.0 (WVTR-BIF), respectively.

Example 13 Atomic Compositions of PECVD Applied OMCTS and HMDSO Coatings

VII.B.4. COC syringe barrel samples made according to the Protocol forForming COC Syringe barrel, coated with OMCTS (according to the Protocolfor Coating COC Syringe Barrel Interior with OMCTS Lubricity layer) orcoated with HMDSO according to the Protocol for Coating COC SyringeBarrel Interior with HMDSO Coating were provided. The atomiccompositions of the coatings derived from OMCTS or HMDSO werecharacterized using X-Ray Photoelectron Spectroscopy (XPS).

VII.B.4. XPS data is quantified using relative sensitivity factors and amodel that assumes a homogeneous layer. The analysis volume is theproduct of the analysis area (spot size or aperture size) and the depthof information. Photoelectrons are generated within the X-raypenetration depth (typically many microns), but only the photoelectronswithin the top three photoelectron escape depths are detected. Escapedepths are on the order of 15-35 Å, which leads to an analysis depth of−50-100 Å. Typically, 95% of the signal originates from within thisdepth.

VII.B.4. The following analytical parameters were used:

-   -   Instrument: PHI Quantum 2000    -   x-ray source: Monochromated Alka 1486.6 eV    -   Acceptance Angle +23°    -   Take-off angle 45°    -   Analysis area 600 μm    -   Charge Correction C1s 284.8 eV    -   Ion Gun Conditions Ar+, 1 keV, 2×2 mm raster    -   Sputter Rate 15.6 Å/min (SiO₂ Equivalent)

VII.B.4. Table 17 provides the atomic concentrations of the elementsdetected. XPS does not detect hydrogen or helium. Values given arenormalized to 100 percent using the elements detected. Detection limitsare approximately 0.05 to 1.0 atomic percent.

VII.B.4. From the coating composition results and calculated startingmonomer precursor elemental percent in Table 17, while the carbon atompercent of the HMDSO-based coating is decreased relative to startingHMDSO monomer carbon atom percent (54.1% down to 44.4%), surprisinglythe OMCTS-based coating carbon atom percent is increased relative to theOMCTS monomer carbon atom percent (34.8% up to 48.4%), an increase of 39atomic %, calculated as follows:

100% [(48.4/34.8)−1]=39 at. %.

Also, while the silicon atom percent of the HMDSO-based coating isalmost unchanged relative to starting HMDSO monomer silicon atom percent(21.8% to 22.2%), surprisingly the OMCTS-based coating silicon atompercent is significantly decreased relative to the OMCTS monomer siliconatom percent (42.0% down to 23.6%), a decrease of 44 atomic %. With boththe carbon and silicon changes, the OMCTS monomer to coating behaviordoes not trend with that observed in common precursor monomers (e.g.HMDSO). See, e.g., Hans J. Griesser, Ronald C. Chatelier, Chris Martin,Zoran R. Vasic, Thomas R. Gengenbach, George Jessup J. Biomed. Mater.Res. (Appl Biomater) 53: 235-243, 2000.

Example 14

Volatile Components from Plasma Coatings (“Outgassing”)

VII.B.4. COC syringe barrel samples made according to the Protocol forForming COC Syringe barrel, coated with OMCTS (according to the Protocolfor Coating COC Syringe Barrel Interior with OMCTS Lubricity layer) orwith HMDSO (according to the Protocol for Coating COC Syringe BarrelInterior with HMDSO Coating) were provided. Outgassing gaschromatography/mass spectroscopy (GC/MS) analysis was used to measurethe volatile components released from the OMCTS or HMDSO coatings.

VII.B.4. The syringe barrel samples (four COC syringe barrels cut inhalf lengthwise) were placed in one of the 1½″ (37 mm) diameter chambersof a dynamic headspace sampling system (CDS 8400 auto-sampler). Prior tosample analysis, a system blank was analyzed. The sample was analyzed onan Agilent 7890A Gas Chromatograph/Agilent 5975 Mass Spectrometer, usingthe following parameters, producing the data set out in Table 18:

-   -   GC Column: 30 m×0.25 mm DB-5MS (J&W Scientific), 0.25 μm film        thickness    -   Flow rate: 1.0 ml/min, constant flow mode    -   Detector: Mass Selective Detector (MSD)    -   Injection Mode: Split injection (10:1 split ratio)    -   Outgassing Conditions: 1½″ (37 mm) Chamber, purge for three hour        at 85° C., flow 60 ml/min    -   Oven temperature: 40° C. (5 min.) to 300° C. @10° C./min.;        -   hold for 5 min. at 300° C.

The outgassing results from Table 18 clearly indicated a compositionaldifferentiation between the HMDSO-based and OMCTS-based lubricity layerstested. HMDSO-based compositions outgassed trimethylsilanol [(Me)₃SiOH]but outgassed no measured higher oligomers containing repeating-(Me)₂SiO— moieties, while OMCTS-based compositions outgassed nomeasured trimethylsilanol [(Me)₃SiOH] but outgassed higher oligomerscontaining repeating -(Me)₂SiO— moieties. It is contemplated that thistest can be useful for differentiating HMDSO-based coatings fromOMCTS-based coatings.

Without limiting the invention according to the scope or accuracy of thefollowing theory, it is contemplated that this result can be explainedby considering the cyclic structure of OMCTS, with only two methylgroups bonded to each silicon atom, versus the acyclic structure ofHMDSO, in which each silicon atom is bonded to three methyl groups.OMCTS is contemplated to react by ring opening to form a diradicalhaving repeating -(Me)₂SiO— moieties which are already oligomers, andcan condense to form higher oligomers. HMDSO, on the other hand, iscontemplated to react by cleaving at one O—Si bond, leaving one fragmentcontaining a single O—Si bond that recondenses as (Me)₃SiOH and theother fragment containing no O—Si bond that recondenses as [(Me)₃Si]₂.

The cyclic nature of OMCTS is believed to result in ring opening andcondensation of these ring-opened moieties with outgassing of higher MWoligomers (26 ng/test). In contrast, HMDSO-based coatings are believednot to provide any higher oligomers, based on the relativelylow-molecular-weight fragments from HMDSO.

Example 15 Density Determination of Plasma Coatings Using X-RayReflectivity (XRR)

VII. B. 4. Sapphire witness samples (0.5×0.5 x 0.1 cm) were glued to theinner walls of separate PET tubes, made according to the Protocol forForming PET tubes. The sapphire witness-containing PET tubes were coatedwith OMCTS or HMDSO (both according to the Protocol for Coating COCSyringe Barrel Interior with OMCTS Lubricity layer, deviating all with2× power). The coated sapphire samples were then removed and X-rayreflectivity (XRR) data were acquired on a PANalytical X'Pertdiffractometer equipped with a parabolic multilayer incident beammonochromator and a parallel plate diffracted beam collimator. A twolayer Si_(w)O_(x)C_(y)H_(z) model was used to determine coating densityfrom the critical angle measurement results. This model is contemplatedto offer the best approach to isolate the true Si_(w)O_(x)C_(y)H_(z)coating. The results are shown in Table 19.

VII. B. 4. From Table 17 showing the results of Example 13, the loweroxygen (28%) and higher carbon (48.4%) composition of OMCTS versus HMDSOwould suggest OMCTS should have a lower density, due to both atomic massconsiderations and valency (oxygen=2; carbon=4). Surprisingly, the XRRdensity results indicate the opposite would be observed, that is, theOMCTS density is higher than HMDSO density.

VII. B. 4. Without limiting the invention according to the scope oraccuracy of the following theory, it is contemplated that there is afundamental difference in reaction mechanism in the formation of therespective HMDSO-based and OMCTS-based coatings. HMDSO fragments canmore easily nucleate or react to form dense nanoparticles which thendeposit on the contact surface and react further on the contact surface,whereas OMCTS is much less likely to form dense gas phase nanoparticles.OMCTS reactive species are much more likely to condense on the contactsurface in a form much more similar to the original OMCTS monomer,resulting in an overall less dense coating.

Example 16 Thickness Uniformity of PECVD Applied Coatings

VII. B. 4. Samples were provided of COC syringe barrels made accordingto the Protocol for Forming COC Syringe barrel and respectively coatedwith SiO_(x) according to the Protocol for Coating COC Syringe BarrelInterior with SiO_(x) or an OMCTS-based lubricity layer according to theProtocol for Coating COC Syringe Barrel Interior with OMCTS Lubricitylayer. Samples were also provided of PET tubes made according to theProtocol for Forming PET Tube, respectively coated and uncoated withSiO_(x) according to the Protocol for Coating Tube Interior with SiO_(x)and subjected to an accelerated aging test. Transmission electronmicroscopy (TEM) was used to measure the thickness of the PECVD-appliedcoatings on the samples. The previously stated TEM procedure of Example4 was used. The method and apparatus described by the SiO_(x) andlubricity layer protocols used in this example demonstrated uniformcoating as shown in Table 20.

Example 17 Outgassing Measurement on COC

VI.B. COC tubes were made according to the Protocol for Forming COCTube. Some of the tubes were provided with an interior barrier coatingof SiO_(x) according to the Protocol for Coating Tube Interior withSiO_(x), and other COC tubes were uncoated. Commercial glass bloodcollection Becton Dickinson 13×75 mm tubes having similar dimensionswere also provided as above. The tubes were stored for about 15 minutesin a room containing ambient air at 45% relative humidity and 70° F.(21° C.), and the following testing was done at the same ambientrelative humidity. The tubes were tested for outgassing following theATC microflow measurement procedure and equipment of Example 8 (anIntelligent Gas Leak System with Leak Test Instrument Model ME2, withsecond generation IMFS sensor, (10μ/min full range), Absolute PressureSensor range: 0-10 Torr, Flow measurement uncertainty: +/−5% of reading,at calibrated range, employing the Leak-Tek Program for automatic dataacquisition (with PC) and signatures/plots of leak flow vs. time). Inthe present case each tube was subjected to a 22-second bulk moisturedegassing step at a pressure of 1 mm Hg, was pressurized with nitrogengas for 2 seconds (to 760 millimeters Hg), then the nitrogen gas waspumped down and the microflow measurement step was carried out for aboutone minute at 1 millimeter Hg pressure.

Again, the outgassing measurement began at about 4 seconds, and a fewseconds later the plots for the uncoated COC tubes and the plots for theSiO_(x) barrier coated tubes clearly diverged, again demonstrating rapiddifferentiation between barrier coated tubes and uncoated tubes. Aconsistent separation of uncoated COC (>2 micrograms at 60 seconds)versus SiO_(x)-coated COC (less than 1.6 micrograms at 60 seconds) wasrealized.

Example 18 Lubricity Layers

VII.B.1.a. COC syringe barrels made according to the Protocol forForming COC Syringe Barrel were coated with a lubricity layer accordingto the Protocol for Coating COC Syringe Barrel Interior with OMCTSLubricity layer. The results are provided in Table 21. The results showthat the trend of increasing the power level, in the absence of oxygen,from 8 to 14 Watts was to improve the lubricity of the coating. Furtherexperiments with power and flow rates can provide further enhancement oflubricity.

Example 19 Lubricity Layers—Hypothetical Example

VII. B. 4. Injection molded cyclic olefin copolymer (COC) plasticsyringe barrels are made according to the Protocol for Forming COCSyringe Barrel. Some are uncoated (“control”) and others are PECVDlubricity coated according to the Protocol for Coating COC SyringeBarrel Interior with OMCTS Lubricity layer (“lubricated syringe”). Thelubricated syringes and controls are tested to measure the force toinitiate movement of the plunger in the barrel (breakout force) and theforce to maintain movement of the plunger in the barrel (plunger slidingforce) using a Genesis Packaging Automated Syringe Force Tester, ModelAST.

VII. B. 4. The test is a modified version of the ISO 7886-1:1993 test.The following procedure is used for each test. A fresh plastic plungerwith elastomeric tip taken from Becton Dickinson Product No. 306507(obtained as saline prefilled syringes) is removed from the syringeassembly. The elastomeric tip is dried with clean dry compressed air.The elastomeric tip and plastic plunger are then inserted into the COCplastic syringe barrel to be tested with the plunger positioned evenwith the bottom of the syringe barrel. The filled syringes are thenconditioned as necessary to achieve the state to be tested. For example,if the test object is to find out the effect of lubricant coating on thebreakout force of syringes after storing the syringes for three months,the syringes are stored for three months to achieve the desired state.

VII. B. 4. The syringe is installed into a Genesis Packaging AutomatedSyringe Force Tester. The tester is calibrated at the start of the testper the manufacturer's specification. The tester input variables areSpeed=100 mm/minute, Range=10,000. The start button is pushed on thetester. At completion of the test, the breakout force (to initiatemovement of the plunger in the barrel) and the plunger sliding force (tomaintain movement) are measured, and are found to be substantially lowerfor the lubricated syringes than for the control syringes.

While the invention has been illustrated and described in detail in thedrawings and foregoing description, such illustration and descriptionare to be considered illustrative or exemplary and not restrictive; theinvention is not limited to the disclosed embodiments. Other variationsto the disclosed embodiments can be understood and effected by thoseskilled in the art and practising the claimed invention, from a study ofthe drawings, the disclosure, and the appended claims. In the claims,the word “comprising” does not exclude other elements or steps, and theindefinite article “a” or “an” does not exclude a plurality. The merefact that certain measures are recited in mutually different dependentclaims does not indicate that a combination of these measures cannot beused to advantage. Any reference signs in the claims should not beconstrued as limiting the scope.

TABLE 1 COATED COC TUBE OTR AND WVTR MEASUREMENT OTR WVTR O—Si O₂ (cc/(mg/ Coating Power Flow Flow Time Tube. Tube. ID (Watts) O—Si (sccm)(sccm) (sec) Day) Day) No 0.215 0.27 Coating A 50 HMDSO 6 90 14 0.0230.07 B 50 HMDSO 6 90 14 0.024 0.10 C 50 HMDSO 6 90 7 0.026 0.10

TABLE 2 COATED PET TUBE OTR AND WVTR MEASUREMENT OTR WVTR O—Si O₂ (cc/(mg/ Coating Power Flow Flow Time Tube. Tube. BIF BIF ID (Watts) O—Si(sccm) (sccm) (sec) Day) Day) (OTR) (WVTR) Uncoated 0.0078 3.65 — —Control SiO_(x) 50 HMDSO 6 90 3 0.0035 1.95 2.2 1.9

TABLE 2A COATED PET TUBE OTR WITH MECHANICAL SCRATCH DEFECTS MechanicalO—Si O₂ Treat Scratch OTR Power Flow Flow Time Length (cc/tube. ExampleO—Si (Watts) (sccm) (sccm) (sec) (mm) day)* OTR BIF Uncoated 0.0052Control Inventive HMDSO 50 6 90 3 0 0.0014 3.7 Inventive HMDSO 50 6 90 31 0.0039 1.3 Inventive HMDSO 50 6 90 3 2 0.0041 1.3 Inventive HMDSO 50 690 3 10 0.0040 1.3 Inventive HMDSO 50 6 90 3 20 0.0037 1.4 *average oftwo tubes

TABLE 3 COATED COC SYRINGE BARREL OTR AND WVTR MEASUREMENT O—Si O₂ OTRWVTR Flow Flow Coating (cc/ (mg/ Syringe O—Si Power Rate Rate TimeBarrel. Barrel. BIF BIF Example Coating Composition (Watts) (sccm)(sccm) (sec) Day) Day) (OTR) (WVTR) A Uncoated 0.032 0.12 Control BSiO_(x) HMDSO 44 6 90 7 0.025 0.11 1.3 1.1 Inventive Example C SiO_(x)HMDSO 44 6 105 7 0.021 0.11 1.5 1.1 Inventive Example D SiO_(x) HMDSO 506 90 7 0.026 0.10 1.2 1.2 Inventive Example E SiO_(x) HMDSO 50 6 90 140.024 0.07 1.3 1.7 Inventive Example F SiO_(x) HMDSO 52 6 97.5 7 0.0220.12 1.5 1.0 Inventive Example G SiO_(x) HMDSO 61 6 105 7 0.022 0.11 1.41.1 Inventive Example H SiO_(x) HMDSO 61 6 120 7 0.024 0.10 1.3 1.2Inventive Example I SiO_(x) HMDZ 44 6 90 7 0.022 0.10 1.5 1.3 InventiveExample J SiO_(x) HMDZ 61 6 90 7 0.022 0.10 1.5 1.2 Inventive Example KSiO_(x) HMDZ 61 6 105 7 0.019 0.10 1.7 1.2 Inventive Example

TABLE 4 SiO_(x) COATING THICKNESS (NANOMETERS) DETECTED BY TEM OxygenHMDSO Flow Thickness Power Flow Rate Rate Sample O—Si (nm) (Watts)(sccm) (sccm) Inventive HMDSO 25-50 39 6 60 Example A Inventive HMDSO20-35 39 6 90 Example B

TABLE 5 ATOMIC RATIOS OF THE ELEMENTS DETECTED (in parentheses,Concentrations in percent, normalized to 100% of elements detected)Plasma Sample Coating Si O C PET Tube - — 0.08 (4.6%) 1 (31.5%) 2.7(63.9%) Comparative Example Polyethylene — 1 (28.6%) 2.5 (71.4%)Terephthal- ate - Calculated Coated PET SiO_(x)    1 (39.1%) 2.4(51.7%)   0.57 (9.2%)  Tube - Inventive Example

TABLE 6 EXTENT OF HOLLOW CATHODE PLASMA IGNITION Hollow Cathode PlasmaStaining Sample Power Time Ignition Result A 25 Watts 7 sec No Ignitionin gas inlet 310, good Ignition in restricted area 292 B 25 Watts 7 secIgnition in gas inlet 310 and poor restricted area 292 C  8 Watts 9 secNo Ignition in gas inlet 310, better Ignition in restricted area 292 D30 Watts 5 sec No Ignition in gas inlet 310 or best restricted area 292

TABLE 7 FLOW RATE USING GLASS TUBES Glass Run #1 Run #2 Average Tube(μg/min.) (μg/min.) (μg/min.) 1 1.391 1.453 1.422 2 1.437 1.243 1.34 31.468 1.151 1.3095 4 1.473 1.019 1.246 5 1.408 0.994 1.201 6 1.328 0.9811.1545 7 Broken Broken Broken 8 1.347 0.909 1.128 9 1.171 0.91 1.0405 101.321 0.946 1.1335 11 1.15 0.947 1.0485 12 1.36 1.012 1.186 13 1.3790.932 1.1555 14 1.311 0.893 1.102 15 1.264 0.928 1.096 Average 1.3431.023 1.183 Max 1.473 1.453 1.422 Min 1.15 0.893 1.0405 Max − Min 0.3230.56 0.3815 Std Dev 0.097781 0.157895 0.1115087

TABLE 8 FLOW RATE USING PET TUBES Uncoated Run #1 Run #2 Average PET(μg/min.) (μg/min.) (μg/min.) 1 10.36 10.72 10.54 2 11.28 11.1 11.19 311.43 11.22 11.325 4 11.41 11.13 11.27 5 11.45 11.17 11.31 6 11.37 11.2611.315 7 11.36 11.33 11.345 8 11.23 11.24 11.235 9 11.14 11.23 11.185 1011.1 11.14 11.12 11 11.16 11.25 11.205 12 11.21 11.31 11.26 13 11.2811.22 11.25 14 10.99 11.19 11.09 15 11.3 11.24 11.27 Average 11.20511.183 11.194 Max 11.45 11.33 11.345 Min 10.36 10.72 10.54 Max − Min1.09 0.61 0.805 Std Dev 0.267578 0.142862 0.195121

TABLE 9 FLOW RATE FOR SiOx COATED PET TUBES Coated Run #1 Run #2 AveragePET (μg/min.) (μg/min.) (μg/min.) 1 6.834 6.655 6.7445 2 9.682 9.513Outliers 3 7.155 7.282 7.2185 4 8.846 8.777 Outliers 5 6.985 6.983 6.9846 7.106 7.296 7.201 7 6.543 6.665 6.604 8 7.715 7.772 7.7435 9 6.8486.863 6.8555 10 7.205 7.322 7.2635 11 7.61 7.608 7.609 12 7.67 7.5277.5985 13 7.715 7.673 7.694 14 7.144 7.069 7.1065 15 7.33 7.24 7.285Average 7.220 7.227 7.224 Max 7.715 7.772 7.7435 Min 6.543 6.655 6.604Max − Min 1.172 1.117 1.1395 Std Dev 0.374267 0.366072 0.365902

TABLE 10 WETTING TENSION MEASUREMENT OF COATED AND UNCOATED TUBESWetting Tension Example Tube Coating (dyne/cm) Reference uncoated glass72 Inventive Example PET tube coated with 60 SiO_(x) according toSiO_(x) Protocol Comparative Example uncoated PET 40 Inventive ExamplePET tube coated 34 according to Hydrophobic layer Protocol ComparativeExample Glass (+silicone fluid) 30 glass syringe, Part No.

TABLE 11 WATER MASS DRAW (GRAMS) Pressurization Time (days) Tube 0 27 4681 108 125 152 231 BD PET 3.0 1.9 1.0 (commercial control) Uncoated PET4.0 3.1 2.7 (internal control) SiO_(x)-Coated PET 4.0 3.6 3.3 (inventiveexample)

TABLE 12 CALCULATED NORMALIZED AVERAGE VACUUM DECAY RATE AND TIME TO 10%VACUUM LOSS Normalized Average Decay rate (delta Time to 10% Loss TubemL/initial mL · da) (months) - Accelerated BD PET 0.0038 0.9 (commercialcontrol) Uncoated PET 0.0038 0.9 (internal control) SiOx-Coated PET0.0018 1.9 (inventive example)

TABLE 13 O—Si O₂ Avg. Power, Flow, Flow, time Force, Sample (Watts)(sccm) (sccm) (sec) (lb.) St. dev. SYRINGE BARRELS WITH LUBRICITY LAYER,ENGLISH UNITS Glass with No No No No 0.58 0.03 Silicone coating coatingcoating coating Uncoated COC No No No No 3.04 0.71 coating coatingcoating coating A 11 6 0 7 1.09 0.27 B 17 6 0 14 2.86 0.59 C 33 6 0 143.87 0.34 D 6 6 90 30 2.27 0.49 Uncoated COC — — — — 3.9 0.6 SiO_(x) onCOC 4.0 1.2 E 11 1.25 0 5 2.0 0.5 F 11 2.5 0 5 2.1 0.7 G 11 5 0 5 2.60.6 H 11 2.5 0 10 1.4 0.1 I 22 5 0 5 3.1 0.7 J 22 2.5 0 10 3.3 1.4 K 225 0 5 3.1 0.4 SYRINGE BARRELS WITH LUBRICITY LAYER, METRIC UNITS Glasssyringe No No No No 0.26 0.01 with sprayed coating coating coatingcoating silicone Uncoated COC No No No No 1.38 0.32 coating coatingcoating coating A 11 6 0 7 0.49 0.12 B 17 6 0 14 1.29 0.27 C 33 6 0 141.75 0.15 D 6 6 90 30 1.03 0.22 Uncoated COC — — — 1.77 0.27 SiO_(x) onCOC, 1.81 0.54 per protocol E 11 1.25 — 5 0.91 0.23 F 11 2.5 — 5 0.950.32 G 11 5 — 5 1.18 0.27 H 11 2.5 — 10 0.63 0.05 I 22 5 — 5 1.40 0.32 J22 2.5 — 10 1.49 0.63 K 22 5 — 5 1.40 0.18

TABLE 14 PLUNGER SLIDING FORCE MEASUREMENTS OF HMDSO- AND OMCTS-BASEDPLASMA COATINGS Coating Coating Si-0 Coating Maximum Normalized TimeFlow Rate Power Force Maximum Example Description Monomer (sec) (sccm)(Watts) (lb, kg.) Force A uncoated 3.3, 1.5 1.0 Control B HMDSO HMDSO 76 8 4.1, 1.9 1.2 Coating C OMCTS OMCTS 7 6 8 1.1, 0.5 0.3 Lubricitylayer D uncoated 3.9, 1.8 1.0 Control E OMCTS OMCTS 7 6 11 2.0, 0.9 0.5Lubricity layer F Two Layer 1 COC 14 6 50 Coating Syringe Barrel +SiO_(x) 2 OMCTS 7 6 8 2.5, 1.1 0.6 Lubricity layer G OMCTS OMCTS 5 1.2511   2, 0.9 0.5 Lubricity layer H OMCTS OMCTS 10 1.25 11 1.4, 0.6 0.4Lubricity layer

TABLE 15 OTR AND WVTR MEASUREMENTS (Prophetic) OTR WVTR (cc/barrel ·(gram/barrel · Sample day) day) COC syringe- Comparative Example 4.3 X3.0 Y PVdC-COC laminate COC syringe- X Y Inventive Example

TABLE 16 OPTICAL ABSORPTION OF SiOx COATED PET TUBES (NORMALIZED TOUNCOATED PET TUBE) Average Coating Absorption (@ Sample Time 615 nm)Replicates St. dev. Reference (uncoated) — 0.002-0.014 4 Inventive A   3sec 0.021 8 0.001 Inventive B 2 × 3 sec 0.027 10 0.002 Inventive C 3 × 3sec 0.033 4 0.003

TABLE 17 ATOMIC CONCENTRATIONS (IN PERCENT, NORMALIZED TO 100% OFELEMENTS DETECTED) AND TEM THICKNESS Plasma Sample Coating Si O CHMDSO-based Si_(w)O_(x)C_(y) 0.76 (22.2%) 1 (33.4%) 3.7 (44.4%) CoatedCOC syringe barrel OMCTS- based Si_(w)O_(x)C_(y) 0.46 (23.6%) 1 (28%)  4.0 (48.4%) Coated COC syringe barrel HMDSO Monomer- Si₂OC₆   2 (21.8%)1 (24.1%)   6 (54.1%) calculated OMCTS Monomer- Si₄O₄C₈  1 (42%) 1(23.2%)   2 (34.8%) calculated

TABLE 18 VOLATILE COMPONENTS FROM SYRINGE OUTGASSING Coating Me₃SiOHHigher SiOMe Monomer (ng/test) oligomers (ng/test) Uncoated COCsyringe - Uncoated ND ND Comparative Example HMDSO-based Coated HMDSO 58ND COC syringe- Comparative Example OMCTS- based Coated OMCTS ND 26 COCsyringe- Inventive Example

TABLE 19 PLASMA COATING DENSITY FROM XRR DETERMINATION Density SampleLayer g/cm³ HMDSO-based Coated Sapphire - Si_(w)O_(x)C_(y)H_(z) 1.21Comparative Example OMCTS- based Coated Sapphire - Si_(w)O_(x)C_(y)H_(z)1.46 Inventive Example

TABLE 20 THICKNESS OF PECVD COATINGS BY TEM TEM TEM TEM Thickness SampleID Thickness I Thickness II III Protocol for Forming 164 nm  154 nm  167nm  COC Syringe Barrel; Protocol for Coating COC Syringe Barrel Interiorwith SiO_(x) Protocol for Forming 55 nm 48 nm 52 nm COC Syringe Barrel;Protocol for Coating COC Syringe Barrel Interior with OMCTS Lubricitylayer Protocol for 28 nm 26 nm 30 nm Forming PET Tube; Protocol forCoating Tube Interior with SiO_(x) Protocol for — — — Forming PET Tube(uncoated)

TABLE 21 OMCTS LUBRICITY LAYER PERFORMANCE (English Units) AveragePercent Plunger Force OMCTS Force Reduction Power Flow Sample (lbs.)*(vs uncoated) (Watts) (sccm) Comparative 3.99 — — — (no coating) SampleA 1.46 63% 14 0.75 Sample B 1.79 55% 11 1.25 Sample C 2.09 48% 8 1.75Sample D 2.13 47% 14 1.75 Sample E 2.13 47% 11 1.25 Sample F 2.99 25% 80.75 *Average of 4 replicatesAbove force measurements are the average of 4 samples.

1. A medical device comprising a substrate defining a contact surfacefor contact between the substrate and a fluid or tissue; and a lubricitylayer deposited on the contact surface and configured to provide a lowersliding force or breakout force for the contact surface than for theuncoated substrate; the lubricity layer having one of the followingatomic ratios, measured by X-ray photoelectron spectroscopy (XPS),Si_(w)O_(x)C_(y) or Si_(w)N_(x)C_(y), where w is 1, x in this formula isfrom about 0.5 to 2.4, and y is from about 0.6 to about 3; the lubricitylayer having a thickness by transmission electron microscopy (TEM)between 10 and 1000 nm; the lubricity layer deposited by plasma enhancedchemical vapor deposition (PECVD) under conditions effective to form acoating from a precursor selected from a linear siloxane, a monocyclicsiloxane, a polycyclic siloxane, a polysilsesquioxane, a linearsilazane, a monocyclic silazane, a polycyclic silazane, apolysilsesquiazane, a silatrane, a silquasilatrane, a silproatrane, anazasilatrane, an azasilquasiatrane, an azasilproatrane, or a combinationof any two or more of these precursors.
 2. The medical device of claim1, in which the precursor is selected from a monocyclic siloxane, apolycyclic siloxane, a polysilsesquioxane, a monocyclic silazane, apolycyclic silazane, a polysilsesquiazane, a silatrane, asilquasilatrane, a silproatrane, an azasilatrane, an azasilquasiatrane,an azasilproatrane, or a combination of any two or more of theseprecursors.
 3. The medical device of claim 1, in which the precursorcomprises hexamethyldisiloxane, octamethyltrisiloxane,decamethyltetrasiloxane, hexamethylcyclotrisiloxane,octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane, a poly(methylsilsesquioxane) according tothe T₈ cube formula:

in which each R is methyl, a poly(Methyl-Hydridosilsesquioxane)according to the T₈ cube formula, in which 90% of the R groups aremethyl and 10% are hydrogen atoms, methyltrimethoxysilane, or acombination of any two or more of these.
 4. The medical device of claim1, in which the precursor comprises octamethylcyclotetrasiloxane(OMCTS).
 5. The medical device of claim 1, in which the precursorconsists essentially of octamethylcyclotetrasiloxane (OMCTS).
 6. Themedical device of claim 1, in which the contact surface is a materialcontacting surface of a medical device selected from: ACL/PCLReconstruction System Adapter Adhesion barrier Agar Petri dishesAnesthesia unit Anesthesia ventilators Angiographic Catheter Anklereplacements Aortic valve replacement Apnea monitor Applicator Argonenhanced coagulation unit Artificial facet replacement Artificial heartArtificial heart valve Artificial organ Artificial pacemaker Artificialpancreas Artificial urinary bladder Aspirator Atherectomy catheterAuditory brainstem implant Auto transfusion unit Bag Balloon CatheterBare-metal stent Beaker bileaflet valve Biliary Stent Bio implantBioceramic device Bioresorbable stent Biphasic Cuirass Ventilation BloodCulture device Blood sample cassette Blood Sampling Systems Bottle Brainimplant Breast implant Breast pump Buccal sample cassette Buttockaugmentation Caged-ball valve Cannulated Screw Capillary BloodCollection device Capsular contracture Cardiac Catheter Cardiacdefibrillator, external or internal Cardiac Output Injectate Kit & CableCardiac prostheses/valves Cardiac shunt Catheter Cell lifters Cellscraper Cell spreader Central Venous Catheter Centrifuge componentCerebral shunt CHD Stent Chemical transfer pump Chin augmentation Chinsling Cochlear implant Collection and Transport device Colonic StentCompression pump Connector Container Contraceptive implant corneaimplant Coronary stent Cotrel-Dubousset instrumentation Cover glassesCranio Maxillofacial Implant Cryo/Freezer boxes Dehydrated Culture Mediadevice Deltec Cozmo Dental implant Depression microscopic slide Dewarflask DHS/DCS & Angled Blade Plates Diabetes accessories Diaphragm pumpsDiaphragmatic pacemaker Direct Testing and Serology device DisposableDomes and Kits Double Channel Catheter Double-Lumen CatheterDrug-Eluting Stent Duodenal Stent Dynamic compression plate Dynamic hipscrew Elastomeric pump Elbow replacements Elbowed CatheterElectrocardiograph (ECG) Electrode Catheter Electroencephalograph (EEG).Electronic thermometer Electrosurgical units Endoscopes Enteral feedingpumps Environmental Systems devices Esophageal stent External FixatorsExternal pacemaker Female Catheter Fetal monitors Film Flat microscopicslide Flow-restricted, oxygen-powered ventilation device FluidAdministration Products Fluid-Filled Catheter Foley Catheter ForcepsGlaucoma valve Goggles Gouley Catheter grafts Grommets Gruentzig BalloonCatheter Harrington rod Heart valves Heart-lung machine HeartMate leftventricular assist device Hip Prosthesis Hip replacement Hip resurfacingHolders Human-implantable RFID chips Hypoxicator Identification andSusceptibility devices Implanon Implant (medicine) Implantablecardioverter-defibrillator Implantable defibrilators Implantable DeviceImplantable Gastric Stimulation Incubators Incubators In-DwellingCatheter Infusion Sets Inhaler Insulin pen Insulin pump InterlockingNail Internal fixation Intra-aortic balloon pump Intramedullary rodIntrathecal pump Intravenous Catheter Invasive blood pressure units Ironlung IV Adapter IV Catheters IV Connectors IV Flush Syringes IV ProductsIV Site Maintenance devices IV Stopcocks Joint replacement Jointreplacement of the hand Keratometer Kirschner wire Knee cartilagereplacement therapy Knee replacement Lancet Laparoscopic insufflatorsLarge Fragment Implants Lensometer Liquid ventilator Lyticbacteriophages Medical grafting Medical Pumps Medical ventilatorMicrobiology Equipment and Supplies Microbiology Testing devicesMicrochip implant (human) Microscopic Slide Microtiter plate MidlineCatheter Mini dental implants Mini Fragment Implants MinimplantsMolecular Diagnostics device Mycobacteria Testing devices Nails, Wires &Pins Needleless IV Connectors Nelaton urinary catheter Norplantimplantable birth control device O'Neil Aspirating and Irrigating NeedleO'Neil Balloon Infuser O'Neil Intermittent urinary catheter Orthopedicimplant Osseointegration implant Oxinium replacement joint materialPacemakers Pacing Catheter Pain management pumps Palatal obturatorPancreatic Stent Penile prosthesis Penis enlargement device Peripheralstents Peripherally Inserted Central Catheter (PICC) Peristaltic pumpsPeritoneovenous shunt Petri dishes Phonocardiographs Phototherapy unitsPipette Polyaxial screw Port (medical) Portacaval shunt Positive airwaypressure device Prepared Media devices Pressure Accessories and CablesPressure Transducers Prostatic Catheter Prostatic stents PulmonaryArtery Catheters Pulse oximeters radiant warmers Radiation-therapymachines Razor Blades re-constructive prosthesis Right-to-left shuntSacral nerve stimulator Safety Supplies Sample collection containerSample collection tube Sample Collection/Storage Device Self-expandablemetallic stent Self-Retaining Catheter Shaker flask Shoulder replacementShunt (medical) skin implant Small Fragment Implants Snare CatheterSphygmomanometers Spinal Cord Stimulator Spine Surgery Stains andReagents Static Control Supplies Stent graft Stents Sterility SuppliesSterilizers Stirrers Subdermal implant Surgical drill and saws Surgicalmicroscope sutures Swabs Swan-Ganz Catheter Syringe driver Temperaturemonitor Tenckhoff Catheter Tiemann Catheter tilting-disk valves Tissuegrinder Toposcopic Catheter Transdermal implant Tubing Tubing linksTwo-Way Catheter Ultrasonic nebulizer Ultrasound sensorsUnicompartmental knee arthroplasty Ureteral Catheter Ureteral stentUrethral Catheter Urinary Catheter Urine sample cassette Vascular ringconnector Vascular stent Ventilator Ventricular assist device Vertebralfixation Winged Catheter, or X-ray diagnostic equipment.
 7. The medicaldevice of claim 1, in which the contact surface is a material contactingsurface of a medical device selected from a: Lancet; Catheter; Scalpel;Saw blade; Suture; Surgical staple; IV connector; or Shunt.
 8. A medicaldevice comprising a substrate defining a contact surface for contactbetween the substrate and a fluid or tissue; and a barrier layerdeposited on the contact surface and configured to reduce thetransmission of a fluid to or from the contact surface; the barrierlayer having one of the following atomic ratios, measured by X-rayphotoelectron spectroscopy (XPS), SiO_(x) or SiN_(x), where x is fromabout 0.5 to 2.4; the barrier layer having a thickness by transmissionelectron microscopy (TEM) between 1 and 1000 nm; the barrier layerdeposited by plasma enhanced chemical vapor deposition (PECVD) underconditions effective to form a coating from a precursor selected from alinear siloxane, a monocyclic siloxane, a polycyclic siloxane, apolysilsesquioxane, a linear silazane, a monocyclic silazane, apolycyclic silazane, a polysilsesquiazane, a silatrane, asilquasilatrane, a silproatrane, an azasilatrane, an azasilquasiatrane,an azasilproatrane, or a combination of any two or more of theseprecursors.
 9. The medical device of claim 8, in which the contactsurface is a material contacting surface of a medical device selectedfrom: ACL/PCL Reconstruction System Adapter Adhesion barrier Agar Petridishes Anesthesia unit Anesthesia ventilators Angiographic CatheterAnkle replacements Aortic valve replacement Apnea monitor ApplicatorArgon enhanced coagulation unit Artificial facet replacement Artificialheart Artificial heart valve Artificial organ Artificial pacemakerArtificial pancreas Artificial urinary bladder Aspirator Atherectomycatheter Auditory brainstem implant Auto transfusion unit Bag BalloonCatheter Bare-metal stent Beaker bileaflet valve Biliary Stent Bioimplant Bioceramic device Bioresorbable stent Biphasic CuirassVentilation Blood Culture device Blood sample cassette Blood SamplingSystems Bottle Brain implant Breast implant Breast pump Buccal samplecassette Buttock augmentation Caged-ball valve Cannulated ScrewCapillary Blood Collection device Capsular contracture Cardiac CatheterCardiac defibrillator, external or internal Cardiac Output Injectate Kit& Cable Cardiac prostheses/valves Cardiac shunt Catheter Cell liftersCell scraper Cell spreader Central Venous Catheter Centrifuge componentCerebral shunt CHD Stent Chemical transfer pump Chin augmentation Chinsling Cochlear implant Collection and Transport device Colonic StentCompression pump Connector Container Contraceptive implant corneaimplant Coronary stent Cotrel-Dubousset instrumentation Cover glassesCranio Maxillofacial Implant Cryo/Freezer boxes Dehydrated Culture Mediadevice Deltec Cozmo Dental implant Depression microscopic slide Dewarflask DHS/DCS & Angled Blade Plates Diabetes accessories Diaphragm pumpsDiaphragmatic pacemaker Direct Testing and Serology device DisposableDomes and Kits Double Channel Catheter Double-Lumen CatheterDrug-Eluting Stent Duodenal Stent Dynamic compression plate Dynamic hipscrew Elastomeric pump Elbow replacements Elbowed CatheterElectrocardiograph (ECG) Electrode Catheter Electroencephalograph (EEG)Electronic thermometer Electrosurgical units Endoscopes Enteral feedingpumps Environmental Systems devices Esophageal stent External FixatorsExternal pacemaker Female Catheter Fetal monitors Film Flat microscopicslide Flow-restricted, oxygen-powered ventilation device FluidAdministration Products Fluid-Filled Catheter Foley Catheter ForcepsGlaucoma valve Goggles Gouley Catheter grafts Grommets Gruentzig BalloonCatheter Harrington rod Heart valves Heart-lung machine HeartMate leftventricular assist device Hip Prosthesis Hip replacement Hip resurfacingHolders Human-implantable RFID chips Hypoxicator Identification andSusceptibility devices Implanon Implant (medicine) Implantablecardioverter-defibrillator Implantable defibrilators Implantable DeviceImplantable Gastric Stimulation Incubators Incubators In-DwellingCatheter Infusion Sets Inhaler Insulin pen Insulin pump InterlockingNail Internal fixation Intra-aortic balloon pump Intramedullary rodIntrathecal pump Intravenous Catheter Invasive blood pressure units Ironlung IV Adapter IV Catheters IV Connectors IV Flush Syringes IV ProductsIV Site Maintenance devices IV Stopcocks Joint replacement Jointreplacement of the hand Keratometer Kirschner wire Knee cartilagereplacement therapy Knee replacement Lancet Laparoscopic insufflatorsLarge Fragment Implants Lensometer Liquid ventilator Lyticbacteriophages Medical grafting Medical Pumps Medical ventilatorMicrobiology Equipment and Supplies Microbiology Testing devicesMicrochip implant (human) Microscopic Slide Microtiter plate MidlineCatheter Mini dental implants Mini Fragment Implants MinimplantsMolecular Diagnostics device Mycobacteria Testing devices Nails, Wires &Pins Needleless IV Connectors Nelaton urinary catheter Norplantimplantable birth control device O'Neil Aspirating and Irrigating NeedleO'Neil Balloon Infuser O'Neil Intermittent urinary catheter Orthopedicimplant Osseointegration implant Oxinium replacement joint materialPacemakers Pacing Catheter Pain management pumps Palatal obturatorPancreatic Stent Penile prosthesis Penis enlargement device Peripheralstents Peripherally Inserted Central Catheter (PICC) Peristaltic pumpsPeritoneovenous shunt Petri dishes Phonocardiographs Phototherapy unitsPipette Polyaxial screw Port (medical) Portacaval shunt Positive airwaypressure device Prepared Media devices Pressure Accessories and CablesPressure Transducers Prostatic Catheter Prostatic stents PulmonaryArtery Catheters Pulse oximeters radiant warmers Radiation-therapymachines Razor Blades re-constructive prosthesis Right-to-left shuntSacral nerve stimulator Safety Supplies Sample collection containerSample collection tube Sample Collection/Storage Device Self-expandablemetallic stent Self-Retaining Catheter Shaker flask Shoulder replacementShunt (medical) skin implant Small Fragment Implants Snare CatheterSphygmomanometers Spinal Cord Stimulator Spine Surgery Stains andReagents Static Control Supplies Stent graft Stents Sterility SuppliesSterilizers Stirrers Subdermal implant Surgical drill and saws Surgicalmicroscope sutures Swabs Swan-Ganz Catheter Syringe driver Temperaturemonitor Tenckhoff Catheter Tiemann Catheter tilting-disk valves Tissuegrinder Toposcopic Catheter Transdermal implant Tubing Tubing linksTwo-Way Catheter Ultrasonic nebulizer Ultrasound sensorsUnicompartmental knee arthroplasty Ureteral Catheter Ureteral stentUrethral Catheter Urinary Catheter Urine sample cassette Vascular ringconnector Vascular stent Ventilator Ventricular assist device Vertebralfixation Winged Catheter, or X-ray diagnostic equipment.
 10. The medicaldevice of claim 8, in which the contact surface is a material contactingsurface of a medical device selected from: Anesthesia ventilatorsAdapters Ankle replacements Artificial pacemaker Artificial pancreasAtherectomy catheter Auditory brainstem implant Buccal sample cassettesCapillary Blood Collection devices Cell lifters Cell scrapers Cellspreaders Centrifuge components Cochlear implant Containers corneaimplants Cover glasses Dehydrated Culture Media devices Depressionmicroscopic slides Direct Testing and Serology devices Drug-ElutingStents Films Flat microscopic slides Glaucoma valve Goggles HipProsthesis Hip replacements Implant (medicine) Implantable DevicesInhaler Insulin pen Insulin pump IV Adapters IV Connectors Jointreplacement of the hand Joint replacements Knee cartilage replacementtherapy Knee replacements Lancets Medical grafting Medical ventilatorMicrobiology Equipment and Supplies Microchip implant (human)Microscopic Slides Microtiter plates Molecular Diagnostics devicesMycobacteria Testing devices Needleless IV Connectors Norplantimplantable birth control device Orthopedic implants PeripherallyInserted Central Catheter (PICC) Peritoneovenous shunt Petri dishesPipettes Portacaval shunt Prostatic stents Razor Blades re-constructiveprosthesis Right-to-left shunt Sacral nerve stimulator Sample collectioncontainers Sample collection tubes Sample Collection/Storage DevicesSelf-expandable metallic stent Shaker flasks Shoulder replacements Shunt(medical) skin implants Stains and Reagents Static Control SuppliesStent grafts Stents Subdermal implant Surgical microscope sutures Tissuegrinders Transdermal implant Ultrasonic nebulizers Unicompartmental kneearthroplasty Ureteral stents Urine sample cassettes Vascular ringconnector Vascular stents.
 11. The medical device of claim 8, in whichthe contact surface is a material contacting surface of a medical deviceselected from: Anesthesia ventilators Medical grafting DehydratedCulture Media devices IV Connectors Tissue grinders Flat microscopicslides Buccal sample cassettes Capillary Blood Collection devicesContainers Inhaler Insulin pen Insulin pump IV Adapters Pipettes Shakerflasks Urine sample cassettes Cell lifters Cell scrapers Cell spreaderscornea implants Cover glasses Depression microscopic slides DirectTesting and Serology devices Microbiology Equipment and SuppliesMicroscopic Slides Microtiter plates Molecular Diagnostics devicesCochlear implant Petri dishes Sacral nerve stimulator Centrifugecomponents Artificial pacemaker Artificial pancreas Glaucoma valveMycobacteria Testing devices Peritoneovenous shunt Portacaval shuntFilms Shoulder replacements Unicompartmental knee arthroplastyre-constructive prosthesis Joint replacement of the hand Jointreplacements Knee cartilage replacement therapy Knee replacementsSurgical microscope Shunt (medical) skin implants Right-to-left shuntStatic Control Supplies Sample collection containers Sample collectiontubes; or Sample Collection/Storage Devices.
 12. A contact surfacehaving a hydrophobic layer having the composition: SiO_(x)C_(y) orSiN_(x)C_(y), where x in this formula is from about 0.5 to 2.4 and y isfrom about 0.6 to about 3, of the type made by: providing a precursorselected from a linear siloxane, a monocyclic siloxane, a polycyclicsiloxane, a polysilsesquioxane, an alkyl trimethoxysilane, a linearsilazane, a monocyclic silazane, a polycyclic silazane, apolysilsesquiazane, or a combination of any two or more of theseprecursors; applying the precursor to a contact surface under conditionseffective to form a coating; and polymerizing or crosslinking thecoating, or both, to form a hydrophobic contact surface having a highercontact angle than the untreated contact surface.
 13. The contactsurface of claim 10, in which the precursor compriseshexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane,hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, asilatrane, a silquasilatrane, a silproatrane, an azasilatrane, anazasilquasiatrane, an azasilproatrane, SST-eM01poly(methylsilsesquioxane), in which each R is methyl, SST-3 MH1.1poly(Methyl-Hydridosilsesquioxane), in which 90% of the R groups aremethyl and 10% are hydrogen atoms, methyl trimethoxysilane, or acombination of any two or more of these.
 14. The contact surface ofclaim 10, in which the precursor comprises octamethylcyclotetrasiloxane.15. The contact surface of claim 10, in which the contact surface is amaterial contacting surface of a medical device selected from: ACL/PCLReconstruction System Adapter Adhesion barrier Agar Petri dishesAnesthesia unit Anesthesia ventilators Angiographic Catheter Anklereplacements Aortic valve replacement Apnea monitor Applicator Argonenhanced coagulation unit Artificial facet replacement Artificial heartArtificial heart valve Artificial organ Artificial pacemaker Artificialpancreas Artificial urinary bladder Aspirator Atherectomy catheterAuditory brainstem implant Auto transfusion unit Bag Balloon CatheterBare-metal stent Beaker bileaflet valve Biliary Stent Bio implantBioceramic device Bioresorbable stent Biphasic Cuirass Ventilation BloodCulture device Blood sample cassette Blood Sampling Systems Bottle Brainimplant Breast implant Breast pump Buccal sample cassette Buttockaugmentation Caged-ball valve Cannulated Screw Capillary BloodCollection device Capsular contracture Cardiac Catheter Cardiacdefibrillator, external or internal Cardiac Output Injectate Kit & CableCardiac prostheses/valves Cardiac shunt Catheter Cell lifters Cellscraper Cell spreader Central Venous Catheter Centrifuge componentCerebral shunt CHD Stent Chemical transfer pump Chin augmentation Chinsling Cochlear implant Collection and Transport device Colonic StentCompression pump Connector Container Contraceptive implant corneaimplant Coronary stent Cotrel-Dubousset instrumentation Cover glassesCranio Maxillofacial Implant Cryo/Freezer boxes Dehydrated Culture Mediadevice Deltec Cozmo Dental implant Depression microscopic slide Dewarflask DHS/DCS & Angled Blade Plates Diabetes accessories Diaphragm pumpsDiaphragmatic pacemaker Direct Testing and Serology device DisposableDomes and Kits Double Channel Catheter Double-Lumen CatheterDrug-Eluting Stent Duodenal Stent Dynamic compression plate Dynamic hipscrew Elastomeric pump Elbow replacements Elbowed CatheterElectrocardiograph (ECG) Electrode Catheter Electroencephalograph (EEG)Electronic thermometer Electrosurgical units Endoscopes Enteral feedingpumps Environmental Systems devices Esophageal stent External FixatorsExternal pacemaker Female Catheter Fetal monitors Film Flat microscopicslide Flow-restricted, oxygen-powered ventilation device FluidAdministration Products Fluid-Filled Catheter Foley Catheter ForcepsGlaucoma valve Goggles Gouley Catheter grafts Grommets Gruentzig BalloonCatheter Harrington rod Heart valves Heart-lung machine HeartMate leftventricular assist device. Hip Prosthesis Hip replacement Hipresurfacing Holders Human-implantable RFID chips HypoxicatorIdentification and Susceptibility devices Implanon Implant (medicine)Implantable cardioverter-defibrillator Implantable defibrilatorsImplantable Device Implantable Gastric Stimulation Incubators IncubatorsIn-Dwelling Catheter Infusion Sets Inhaler Insulin pen Insulin pumpInterlocking Nail Internal fixation Intra-aortic balloon pumpIntramedullary rod Intrathecal pump Intravenous Catheter Invasive bloodpressure units Iron lung IV Adapter IV Catheters IV Connectors IV FlushSyringes IV Products IV Site Maintenance devices IV Stopcocks Jointreplacement Joint replacement of the hand Keratometer Kirschner wireKnee cartilage replacement therapy Knee replacement Lancet Laparoscopicinsufflators Large Fragment Implants Lensometer Liquid ventilator Lyticbacteriophages Medical grafting Medical Pumps Medical ventilatorMicrobiology Equipment and Supplies Microbiology Testing devicesMicrochip implant (human) Microscopic Slide Microtiter plate MidlineCatheter Mini dental implants Mini Fragment Implants MinimplantsMolecular Diagnostics device Mycobacteria Testing devices Nails, Wires &Pins Needleless IV Connectors Nelaton urinary catheter Norplantimplantable birth control device O'Neil Aspirating and Irrigating NeedleO'Neil Balloon Infuser O'Neil Intermittent urinary catheter Orthopedicimplant Osseointegration implant Oxinium replacement joint materialPacemakers Pacing Catheter Pain management pumps Palatal obturatorPancreatic Stent Penile prosthesis Penis enlargement device Peripheralstents Peripherally Inserted Central Catheter (PICC) Peristaltic pumpsPeritoneovenous shunt Petri dishes Phonocardiographs Phototherapy unitsPipette Polyaxial screw Port (medical) Portacaval shunt Positive airwaypressure device Prepared Media devices Pressure Accessories and CablesPressure Transducers Prostatic Catheter Prostatic stents PulmonaryArtery Catheters Pulse oximeters radiant warmers Radiation-therapymachines Razor Blades re-constructive prosthesis Right-to-left shuntSacral nerve stimulator Safety Supplies Sample collection containerSample collection tube Sample Collection/Storage Device Self-expandablemetallic stent Self-Retaining Catheter Shaker flask Shoulder replacementShunt (medical) skin implant Small Fragment Implants Snare CatheterSphygmomanometers Spinal Cord Stimulator Spine Surgery Stains andReagents Static Control Supplies Stent graft Stents Sterility SuppliesSterilizers Stirrers Subdermal implant Surgical drill and saws Surgicalmicroscope sutures Swabs Swan-Ganz Catheter Syringe driver Temperaturemonitor Tenckhoff Catheter Tiemann Catheter tilting-disk valves Tissuegrinder Toposcopic Catheter Transdermal implant Tubing Tubing linksTwo-Way Catheter Ultrasonic nebulizer Ultrasound sensorsUnicompartmental knee arthroplasty Ureteral Catheter Ureteral stentUrethral Catheter Urinary Catheter Urine sample cassette Vascular ringconnector Vascular Stent Ventilator Ventricular assist device Vertebralfixation Winged Catheter, or X-ray diagnostic equipment.
 16. The contactsurface of claim 10, in which the contact surface is a materialcontacting surface of a medical device selected from: Flat microscopicslides Glaucoma valves Mycobacteria Testing devices Peritoneovenousshunts Portacaval shunts Surgical microscope Shunt (medical) skinimplants Right-to-left shunt Static Control Supplies Sample collectioncontainers Sample collection tubes Sample Collection/Storage Devices